Heavy crude conversion catalyst

ABSTRACT

This invention relates to novel catalysts, of two distinct types, useful for the catalytic hydroconversion of the 1050° F.+ hydrocarbon materials contained in heavy crudes and residua such that the resulting product will be suitable for further processing in conventional refinery operations allowing maximization of clean liquid products. Catalysts, which include Group VIB and Group VIII metals, preferably in admixture, and preferably including a Group IVA metal, notably germanium, having certain critical ranges of physical characteristics inclusive of large uniform pore sizes, are used for the conversion, these having been shown to possess improved catalytic activity and selectively for the hydroconversion of the 1050° F.+ materials of the heavy feeds and residua. Novel methods are described for the preparation of such catalysts, as well as for the use of such catalysts. One of the catalysts, i.e., one having properties inclusive of a large number of pores in the 100-275A pore size diameter range, is particularly suitable as a first stage catalyst and the other, which has properties inclusive of a large number of pores in the 100-200A pore size diameter, is especially suitable as a second stage catalyst for use in processing the effluent of said first stage.

RELATED APPLICATIONS

This is a continuation-in-part of Application Ser. No. 440,315 filedFebruary 7, 1974, and now abandoned which application is herewithincorporated by reference.

Other related applications which describe new and improved catalysts,and hydroconversion processes, or processes for cracking the 1050° F.+hydrocarbon portion of heavy whole crudes and residua to yield therefromlighter boiling usable products, particularly from unconventional heavycrudes and residua which contain appreciable amounts of sulfur andnitrogen, high quantities of the so-called heavy metals, e.g., nickeland vanadium, as well as high "Con. carbon," high carbon-to-hydrogenratios, high asphaltenes, ash, sand, scale, and the like, areApplication Ser. No. 533,314, filed Dec. 16, 1974, which is acontinuation-in-part of abandoned Application Ser. No. 440,303, filedFebruary 7, 1974, by G. P. Hamner; Application Ser. No. 533,299, filedDec. 16, 1974, which is a continuation-in-part of abandoned ApplicationSer. No. 440,285 by W. F. Arey, Jr. et al; Application Ser. No. 533,300,filed Dec. 16, 1974, which is a continuation-in-part of abandonedApplication Ser. No. 440,290 by W. F. Arey, Jr. et al; Application Ser.No. 533,311, filed Dec. 16, 1974, which is a continuation-in-part ofabandoned Application Ser. No. 440,302 by W. F. Arey, Jr. et al;Application Ser. No. 533,312, filed December 16, 1974, which is acontinuation-in-part of abandoned Application Ser. No. 440,316 by W. J.Mattox; Application Ser. No. 533,313, filed Dec. 16, 1974, which is acontinuation-in-part of abandoned Application Serial No. 440,302 by F.M. Long et al; and Application Ser. No. 533,331, filed December 16,1974, which is a continuation-in-part of Application Serial No. 440,301by W. F. Arey, Jr. et al.

The hydrotreating of hydrocarbon or hydrocarbonaceous feedstocks,including particularly heavy petroleum crudes and residua, is not new,and such processes are widely disclosed in the patent literature. Themolecular make-up of such feedstocks is often such that they containconsiderable amounts of heavy oils, resins, nondistillable asphaltenes,i.e., pentane (C₅) or heptane insoluble, or high molecular weight cokeprecursors, and the like, which contain high nitrogen, sulfur, oxygenand metallo-organic complexes, or metal contaminants which, whensubjected to heat, coagulate, polymerize or decompose and creatematerials difficult to further process. In the past, the lower molecularweight or gas oil portion of such feedstocks has been catalyticallyconverted and upgraded to high value fuels, while the heavy ends or1050° F.+ materials were split out, then generally used as low gradefuel or as asphaltic materials. The 1050° F.+ material, often termed"the bottom of the barrel," is of low commercial value, even less thanan equivalent quantity of raw crude. Recent economics, however, havemade it necessary to hydrotreat even the 1050° F.+ residues todesulfurize these materials, due to the environmental hazards created byburning the sulfur-containing fuels. Whereas the literature describes anumber of catalytic hydrodesulfurization processes for the treatment ofsuch feedstocks, hydrocarbon conversion is minimized essentially to thatrequired for the breaking of carbon-sulfur bonds of the relatively lowmolecular weight hydrocarbons, with subsequent hydrogenation of thesulfur moieties to eliminate the sulfur which is evolved as hydrogensulfide gas.

Processes for the conversion of feeds containing 1050° F.+ hydrocarbonmaterials to lower molecular weight hydrocarbons at high temperaturesand pressures are likewise not unknown. Present processes for suchconversion generally involve coking, which is industry's primaryupgrading process. In one such process, the excessive carbon in the feedis coked and then removed as high sulfurmetals coke, and the coke thengasified to make a fuel gas. Thermally cracked liquids are concurrentlyproduced. In another such process, the entire feed is gasified to make asubstitute natural gas. The coking processes, however, have certainlimitations, the most important being that large quantities of sour cokeand gas are produced at the expense of liquids, and it is difficult todispose of sour coke. Processes are also known for the catalytichydroconversion of crudes or feeds which contain 1050° F.+ hydrocarbonmaterials. For example, in Johanson's U.S. Pat. No. 2,987,465, ahydrocarbon feed and gas are passed upwardly through an ebullating bedof particulate catalytic solids. The process is thus conducted underconditions which establish a random motion of the catalytic particles inthe liquid without carrying the solids out of the reactor. Based on thesolid size and density of the catalyst particles, and liquid density,velocity and viscosity, the mass of particulate solids is expanded fromabout 10 percent greater volume than the settled state of the mass toperhaps two or three times the settled volume. While such process hasbeen found useful in the treatment of such feeds, it too has itslimitations. Thus, there are certain disadvantages associated with theactivity of the catalysts used in such process. For example, inprocessing residua, inter alia, a tarry, sticky material is formed uponand apparently absorbed by the catalyst particles, this all too rapidlyfouling the catalyst. Conglomeration of the catalyst particles produceschanneling and lowering of catalyst performance.

It is thus particularly difficult to treat crudes or residuas whichcontain large amounts of 1050° F.+ hydrocarbons, even where there is nosignificant conversion of hydrocarbon to lower boiling products. Evenhydrodesulfurization processes, which have been recognized aspotentially useful for effecting the removal of sulfur from such fuels,have been relatively ineffective for the hydrotreatment of residua. Highoperating costs associated with the relatively high pressures required,high hydrogen consumption and short catalyst life, inter alia, havehindered commercial utilization of such processes. The hydroconversionof 1050° F.+ hydrocarbon materials to lower boiling, more usefulhydrocarbons presents an acutely more difficult problem.

Supply and demand considerations, nonetheless, make it imperative thatnew and improved methods be developed for conversion of the heavy wholecrudes and residua, particularly for the conversion of the 1050° F.+portion of these materials. In fact, it is imperative that processes bedeveloped which make it practical for the hydroconversion of new typesof heavy crudes and residua which contain great amounts of the 1050° F.+materials, which crudes and residua cannot be handled by presenthydroconversion processes. It is thus known that within a few yearsperhaps one-half of the consumption of energy in this country may bederived from particularly unconventional materials such as Athabasca tarsands, Canadian and Venezuelan heavy oils and Venezuelan heavy tars.These so-called heavy crudes are different from conventional crudes inat least four important aspects, each of which makes hydroconversion ofsuch crudes by present methods entirely unfeasible - viz., they have (1)very high Conradson carbon (i.e., "Con. carbon") or carbon to hydrogenratios (i.e., relatively high carbon and low hydrogen content), (2) veryhigh metals content, particularly as regards the amount of nickel andvanadium, (3) they are ultra-high in their content of materials boilingabove 1050° F., e.g., asphaltenes, and even (4) contain considerableamounts of sand and scale. Properties which readily distinguish thesenew materials from conventional crudes are thus: high metals, highasphaltenes, high carbon:hydrogen ratios, and a high volume percent ofhydrocarbons boiling above 1050° F. The presence of the greater amountsof metals and the higher carbon content of the heavy crudes, inparticular, makes any considerations regarding the processing of thesematerials most difficult and expensive. The high "Con.carbon" andcarbon: hydrogen ratios are considerably higher than those of anypresently usable hydrocarbon liquids.

There is thus a desideratum in the art, dictated in part by an impendingenergy crunch, which makes imperative the development of new andeffective hydroconversion processes, or processes for cracking the 1050°F.+ hydrocarbon portion of heavy whole crudes and residua to yieldtherefrom lighter boiling usable products. There is particular need forcatalytic processes, inclusive of new catalysts and techniques for theirpreparation, which can effectively hydroprocess and convert the 1050°F.+ hydrocarbon portion of these unconventional heavy crudes and residuawhich contain appreciable amounts of sulfur and nitrogen, highquantities of the so-called heavy metals, e.g., nickel and vanadium, aswell as high "Con. carbons", high carbon to hydrogen ratios, highasphaltenes, sand, scale and the like, supra.

A primary objective of the present invention, therefore, is to obviatethe several prior art deficiencies, and to supply these several needs.

A particular object is to provide new and improved catalysts,particularly useful in hydrocarbon conversion reactions, particularlyreactions involving the hydroconversion of the 1050° F.+ hydrocarbonportion of heavy crudes and residua.

A further object is to supply new and improved methods for thepreparation of such catalysts.

Another object is to provide a new and improved hydrocarbon conversionprocess, or hydroconversion process useful in converting the 1050° F.+hydrocarbon portion of feeds comprising heavy crudes and residua touseful lower boiling products while simultaneously producing appreciableCon. carbon reduction, hydrodesulfurization, hydrodenitrogenation anddemetallization of the feeds.

These objects and others are achieved in accordance with the presentinvention which embodies

a. novel catalysts which, although they possess certain commoncharacteristics, are of two distinct types as relates to an essentialcombination of properties regarding pore size (or pore sizedistribution), surface area and pore volume, this enabling each toperform its function in a unique manner, a first catalyst providingenhanced selectivity for conversion and demetallization of whole heavycrudes and residua, in the presence of added hydrogen, which containsrelatively large quantities of 1050° F.+ materials, i.e., asphaltenes(C₅ insoluble) and other large hydrocarbon molecules, which areeffectively converted to lower molecular weight products, and a secondcatalyst particularly suitable for the efficient conversion,demetallization and Con. carbon reduction of hydrocarbon materials,particularly of a feed of character similar to the product resultantfrom a hydroconversion process utilizing said first catalyst.Conversion, as used herein, thus requires chemical alteration of the1050° F.+ hydrocarbon molecules to form lower molecular weight moleculesboiling below 1050° F. (i.e., 1050° F.-) and it is measured by theweight decrease in the amount of 1050° F.+ hydrocarbons contained in theoriginal feed times 100, divided by the amount of 1050° F.+ materialoriginally present in the feed. These catalysts in common comprisecatalytically active amounts of a hydrogenation component which includesa Group VIB or Group VIII metal (especially, a Group VIII nonnoblemetal), or both (Periodic Table of the Elements, E. H. Sargent and Co.,Copyright 1962 Dyna-Slide Co.), particularly molybdenum or tungsten ofGroup VIB, and cobalt or nickel of Group VIII, and preferably a GroupVIB and Group VIII metal in admixture one metal with the other, or withother metals, or both, particularly Group IVA metals, composited with arefractory inorganic support, notably a porous, inorganic oxide support,particularly alumina, or more particularly gamma alumina,

i. said first catalyst, hereinafter termed "R-1" catalyst forconvenience, including a combination of properties comprising, when thecatalyst is of size ranging up to one-fiftieth inch average particlesize diameter, at least about 20 percent, preferably at least about 25percent, and more preferably at least about 70 percent of its total porevolume of absolute diameter within the range of about 100A (Angstromunits) to about 200A; when the catalyst is of size ranging from aboutone-fiftieth inch up to one-twenty-fifth inch average particle sizediameter, at least about 15 percent, preferably at least about 20percent, and more preferably at least about 45 percent of its total porevolume of absolute diameter within the range of about 150A to about250A; when the catalyst is of size ranging from about one-twenty-fifthinch to about one-eighth inch average particle size diameter, at leastabout 15 percent, preferably at least about 20 percent, and morepreferably at least about 30 percent of its total more volume ofabsolute diameter within the range of about 175A to about 275A; wherein,in each of these catalysts of differing ranges of particle sizedistributions, the pore volumes resultant from pores of 50A, andsmaller, i.e., 50A-, are minimized; and preferably, while in catalystaverage particle size below one-fiftieth inch, the pore volume resultantfrom pores of diameter above 300A, i.e., 300A+, is minimized, and incatalysts of average particle size above one-fiftieth inch, the porevolume resultant from pores above 350A, i.e., 350A+, is minimized; thesurface areas and pore volumes of the catalysts being interrelated withparticle size, and pore size distributions, surface areas ranging atleast about 200 m² /g to about 600 m² /g, and preferably at least about250 m² /g to about 450 m² /g, with pore volumes ranging from about 0.8to about 3.0 cc/g, and preferably from about 1.1 to about 2.3 cc/g(B.E.T.):

ii. said second catalyst, hereinafter termed "R-2" catalyst forconvenience, over the spectrum of particle sizes ranging to one-eighthinch average particle size diameter, is one including a combination ofproperties comprising at least about 55 percent, and preferably at leastabout 70 percent of its total pore volume of absolute diameter withinthe range of about 100A to about 200A; less than 10 percent, preferablyless than 1 percent of the pore volume results from pores of diameters50A- ; less than about 25 percent, and preferably less than 1 percent ofthe total pore volume results from pores of diameters ranging 300A+;surface areas ranging from about 200 m² /g to about 600 m² /g,preferably from about 250 m² /g to about 350 m² /g, and pore volumesranging from about 0.6 to about 1.5 cc/g, and preferably from about 0.9to about 1.3 cc/g. (B.E.T.):

b. a novel method for the preparation of said R-1 and R-2 catalysts froman aqueous or alcohol synthesis sol comprising dispersing an aluminumhalide in an aqueous or alcohol medium, and adding an organic reagentwhich combines with the halide and removes the halide from solution asan organic halide, with control of water (or alcohol):alumina saltratios, and control and removal of hydrogen halide acid generated withreaction, preferably with the additional incorporation of Group VIIInoble metals or lanthanum or lanthanum series metal salts, or both, toprovide the selective pore size distributions, particularly as relatesto the formation of extrudates, with concurrent optimization of surfacearea and pore volume, as required for the production of R-1 and R-2catalysts; and

c. a conversion process, conducted with said R-1 catalyst, in an initialor first reaction zone comprising one or more stages (and in one or morereactors) wherein a hydrocarbon or hydrocarbonaceous feed, e.g., a coalliquid, whole heavy crude or residua feed, containing 1050° F.+materials, especially one having the following characteristics,

    ______________________________________                                                           Operable                                                                             Preferred                                                              Range  Range                                               ______________________________________                                        Gravity, API         -5 to 20 0-14                                            Heavy Metals (Ni & V), ppm                                                                         5-1000   200-600                                         1050° F.+, Wt.%                                                                             10-100   40-100                                          Asphaltenes (C.sub.5 insolubles), Wt.%                                                             5-50     15-30                                           Con. Carbon, wt.%    5-50     10-30                                           ______________________________________                                    

is contacted, in the presence of hydrogen at severities sufficient toconvert at least about 30 percent by weight and preferably from about 40percent to about 60 percent of the 1050° F.+ materials of the crude orresidua present to 1050° F.- materials, remove at least about 75percent, and preferably from about 80 to about 95 percent, by weight ofthe metals, preferably producing a product having the followingcharacteristics:

    ______________________________________                                                           Operable                                                                             Preferred                                                              Range  Range                                               ______________________________________                                        Gravity, API         14-30    15-25                                           Heavy Metals (Ni & V), ppm                                                                         10-100   40-80                                           1050° F.+, Wt.%                                                                             10-50    25-40                                           Asphaltenes (C.sub.5 insolubles), Wt.%                                                             3-20     5-15                                            Con. Carbon, Wt.%    3-20     5-10                                            ______________________________________                                    

which product is suitable for further contact, in the presence ofhydrogen, in a second or subsequent reaction zone comprising one or morestages (and in one or more reactors) with said R-2 catalyst atseverities sufficient to convert at least about 50 percent, andpreferably from about 60 percent to about 75 percent of the 1050° F.+materials of the crude or residua to 1050° F.- materials, remove atleast about 90 percent, preferably from about 97 percent to about 100percent, by weight of the metals, and reduce Con. carbon from about 50percent to about 100 percent, and preferably from about 75 percent toabout 90 percent, especially to produce a product having the followngcharacteristics:

    ______________________________________                                                           Operable                                                                             Preferred                                                              Range  Range                                               ______________________________________                                        Gravity, API         18-30    20-28                                           Heavy Metals (Ni & V), ppm                                                                         <50      <5                                              1050° F.+, Wt.%                                                                             5-30     10-25                                           Asphaltenes (C.sub.5 insolubles), Wt.%                                                             <3       <1                                              Con. Carbon, Wt.%    <5       <3                                              ______________________________________                                    

In their optimum forms, the absolute pore size diameter, of the R-1catalyst, dependent on particle size, is maximized within the 100-200A,150-250A, and 175-275A ranges, and the R-2 catalyst within the 100-200Arange, respectively. It is not practical, of course, to eliminate thepresence of all pores of sizes which do not fall within these ranges,but methods of preparation are known, particularly methods ofpreparation according to this invention, which does indeed make itpractical to produce catalyst particles of absolute pore size diametershighly concentrated within these desired ranges. The followingtabulations show the pore size distributions, as percent of total porevolume, of marginal and preferred catalysts of this invention:

    ______________________________________                                        R-1 CATALYST                                                                  Distribution of                  More                                         Pore Diameters.sup.(1)                                                                       Marginal Preferred                                                                              Preferred                                    ______________________________________                                        1/500 up to 1/50".sup.(2)                                                     0-50A          <20%     <10%     <2%                                          100-200A       >20%     >25%     >70%                                         300A+          <30%     <25%     <1%                                          Pore Volume, cc/g                                                                            0.8-1.4  0.9-1.5  1.1-1.7                                      Surface Area, m.sup.2 /g                                                                     300-450  310-500  325-550                                      1/50 up to 1/25".sup.(2)                                                      0-50A          <10%     <5%      <1%                                          150-250A       >15%     >20%     >45%                                         350A+          <35%     <30%     <7%                                          Pore Volume, cc/g                                                                            1.1-1.7  1.3-1.9  1.5-2.1                                      Surface Area, m.sup.2 /g                                                                     320-475  340-575  360-600                                      1/25 up to 1/8".sup.(2)                                                       0-50A          <5%      <4%      <3%                                          175-275A       >15%     >20%     >30%                                         350A+          <40%     <35%     <25%                                         Pore Volume, cc/g                                                                            1.3-1.9  1.5-2.1  1.3-2.3                                      Surface Area, m.sup.2 /g                                                                     340-500  350-600  370-650                                      R-2 CATALYST                                                                  Distribution of                  More                                         Pore Diameters.sup.(1)  Preferred                                                                              Preferred                                    1/500 up to 1/8" .sup.(2)                                                     0-50A                   <10%     <1%                                          100-200A                >55%     >70%                                         300A+                   <25%     <1%                                          ______________________________________                                         .sup.(1) Measured by nitrogen adsorption isotherm, wherein nitrogen           adsorbed is at various pressures. Technique described in Ballou, et al,       Analytical Chemistry, Vol. 32, April, 1960, using Aminco Adsorptomat          [(Catalogue No. 4-4680) and Multiple Sample Accessory (Catalogue No.          4-4685) Instruction No. 861-A] which uses the principle of adsorption and     desorption of gas by a catalyst specimen at the boiling point of nitrogen     .sup.(2) Average particle diameter in inches.                            

The R-1 and R-2 catalysts can be the same or different as regards theirspecific chemical composition, qualitatively or quantitatively, thoughcertain different forms of these catalysts have been found to providebetter results when used in the different and preferred modes--viz. whenR-1 is used in an initial or first reaction zone to process heavy crudesor residua, hereinafter referred to as "R-1 service," and when R-2 isused in a second or subsequent reaction zone to process, e.g. theproduct of said initial or first reaction zone (or feed of similarnature), hereinafter referred to as "R-2 service." In general, however,both the R-1 and R-2 catalysts can comprise a composite of a refractoryinorganic support material, preferably a porous inorganic oxide supportwith a metal or compound of a metal, or metals, selected from Group VIBor Group VIII, or both, the metals generally existing as oxides,sulfides, reduced forms of the metal or as mixtures of these and otherforms. Suitably, the composition of the catalysts comprises from about 5to about 50 percent, preferably from about 15 to about 25 percent (asthe oxide) of the Group VIB metal, and from about 1 to about 12 percent,preferably from about 4 to about 8 percent (as the oxide) of the GroupVIII metal, based on the total weight (dry basis) of the composition.The preferred active metallic components, and forms thereof, comprise anoxide or sulfide of molybdenum and tungsten of Group VIB, an oxide orsulfide of nickel or cobalt of Group VIII, preferably a mixture of oneof said Group VIB and one of said Group VIII metals, admixed one withthe other and inclusive of third metal components of Group VIB, VIII andother metals, particularly Group IVA metals. The preferred R-1 and R-2catalysts are constituted of an admixture of cobalt and molybdemum, butin some cases the preferred R-2 catalysts may be comprised of nickel andmolybdenum. The nickel-molybdenum catalyst in R-2 service possesses veryhigh hydrogenation activity and is particularly effective in reducingCon. carbon. Other suitable Group VIB and VIII metals include, forexample, chromium, platinum, palladium, iridium, osmium, ruthenium,rhodium, and the like. The inorganic oxide supports comprise alumina,silica, zirconia, magnesia, boria, phosphate, titania, ceria, thoria,and the like. The preferred support is alumina, preferably gammaalumina, which in R-2 service is preferably stabilized with silica inconcentration ranging from about 0.1 to about 20 percent, preferablyfrom about 10 to about 20 percent, based on the total weight (dry basis)alumina-silica composition (inclusive of metal components). The catalystcomposition can be in the form of beads, aggregates of various particlesizes, extrudates, tablets or pellets, depending upon the type ofprocess and conditions to which the catalyst is to be exposed.

Particularly preferred catalysts are composites of nickel or cobaltoxide with molybdenum, used in the following approximate proportions:from about 1 to about 12 weight percent, preferably from about 4 toabout 8 weight percent of nickel or cobalt oxides; and from about 5 toabout 50 weight percent, preferably from about 15 to about 25 weightpercent of molybdenum oxide on a suitable support, such as alumina. Aparticularly preferred support for R-2 catalyst comprises aluminacontaining from about 10 to about 20 percent silica. The catalyst issulfided to form the most active species.

The Group VIB and Group VIII metal components, admixed one componentwith the other or with a third or greater number of metal components,can be composited or intimately associated with the porous inorganicoxide support or carrier by various techniques known to the art, such asby impregnation of a support with the metals, ion exchange,coprecipitation of the metals with the alumina in the sol or gel form,and the like. For example, a preformed alumina support can beimpregnated by an "incipient wetness" technique, or technique wherein ametal, or metals, is contained in a solution in measured amount and theentire solution is absorbed into the support which is then dried,calcined, etc., to form the catalyst. Also, for example, the catalystcomposite can be formed from a cogel by adding together suitablereagents such as salts of the Group VIB or Group VIII metals, or both,and ammonium hydroxide or ammonium carbonate, and a salt of aluminumsuch as aluminum chloride or aluminum sulfate to form aluminumhydroxide. The aluminum hydroxide containing the salts of the Groups VIBor Group VIII metals, or both, and additional metals if desired can thenbe heated, dried, formed into pellets, or extruded, and then calcined.Catalysts formed from cogels do not possess pore size distribution asuniform as those formed by impregnation methods.

The catalysts can be used in the reaction zones as fixed beds,ebullating beds or in slurry form within beds. When used in the form offixed beds, the particle size diameter of the catalysts generally rangesfrom about 1/32 to about 1/8 inch, preferably about 1/16 inch. When usedas ebullating beds the catalyst generally range about 1/32 inch diameterand smaller, and when used as slurry beds the particle sizes generallyrange from about 100 to about 400 microns. The bulk density of the R-1catalyst generally ranges from about 0.2 to about 0.6 g/cc, preferablyfrom about 0.2 to about 0.5 g/cc, depending on particle size, and thatof the R-2 catalyst ranges from about 0.3 to about 0.8 g/cc, preferablyfrom about 0.35 to about 0.55 g/cc.

The catalysts of this invention further comprise a metal, or metals, ofGroup IVA, or compounds thereof. The catalysts will thus comprisegermanium, tin, or lead, or admixture of such metals with each other orwith other metals, or both, in combination with the Group VIB or GroupVIII metals, or admixture thereof. The Group IVA metals act as promotersfor R-1 and R-2 catalysts in enhancing the rate of demetallization of afeed. Of the Group IVA metals, germanium is particularly preferred.Suitably, the Group IVA metal comprises from about 0.01 to about 10percent, preferably from about 2.0 to about 5 percent of the catalyst,based on the total weight (dry basis) of the composition. The Group IVAmetals must be incorporated within the catalyst by impregnation.

A feature of both the R-1 and R-2 catalysts is that each is of very highsurface area and contains ultra-high pore volume, this providing anextremely great number of active metal sites. This, in combination withthe selected pore size distributions of the R-1 and R-2 catalysts,provides catalysts admirably suitable for the demetallization andhydroconversion of feeds of the characteristics described, which feedsusually contain additional high concentrations of sulfur and nitrogen.In R-1 service, in utilizing R-1 catalyst in its most preferred form,the number of pores ranging between about 100-275A absolute pore sizediameter is maximized, dependent on particle size, as is surface areaand pore volume consistent with practical catalyst preparationprocedures and with regard to the particle crush strength requirementsof the process. Moreover, the number of pores which are smaller than50A, and preferably those greater than about 300A, or about 350A whenthe average particle size diameter exceeds about 1/50 inch, areminimized. R-1 catalyst of such character has thus proven outstanding,even under the stringent requirements of R-1 service, in retainingconsiderable quantities of heavy metals while yet remaining active overextraordinarily long periods. For Example, the R-1 catalyst, whenoperated at a 700° F. start-of-run temperature (SOR), has been shownsuitable for maintaining 1050° F.+ conversion levels ranging from about20 to about 40 percent, and higher, for periods ranging up to about 70days, and longer. In fact, this catalyst, at the end of such period, hasbeen found to retain over 150 percent of its own weight of heavy metalsfrom whole heavy crudes and residua feeds. Moreover, while accomplishingthis, the R-1 catalyst also effectively removes much of the sulfur andnitrogen in hydrodesulfurization and hydrodenitrogenation reactions. Forexample, whole heavy crudes and residua of the type characterized oftencontain from about 2 to about 7 weight percent, usually from about 3 toabout 6 percent sulfur, and often from about 0.2 to about 0.8 percent,usually from about 0.3 to about 0.7 percent nitrogen. Generally, fromabout 75 to about 95 percent of the sulfur, and from about 25 to about60 percent of the nitrogen can be effectively removed from such heavycrudes and residua in R-1 service while obtaining high conversion. Theproduct of such reaction, unlike the original feed processed over theR-1 catalyst, is now suitable as feed to a coker to provide greateryields of C₃ ⁺ liquid product than would otherwise have been possible bycoking the original feed, and the coke product is less sour and lesscontaminated by heavy metals. For example, it has been found that byoperating the R-1 catalyst at a start-of-run (SOR) temperature of about700° F. at a low space velocity of about 0.25-0.50 V/H/V, a product isobtained which is highly suitable for coking. Compared to coking of theraw whole crude or residuum, the C₃ ⁺ liquid product yield is increasedfrom 86 to 97 vol.% and the coke yield is decreased some 70%. Theproduct coke contains only 2.5 wt.% sulfur compared to 5.9% sulfur cokefrom coking of the raw feed.

The product of the reaction conducted at a space velocity of 0.25V/Hr./V is also highly suited for processing in a resid catalyticcracking operation. The raw feed contains too much heavy metals and Concarbon for conventional catalytic cracking. The product, on the otherhand, is low enough in heavy metals and Con carbon to be converted in aresid catalytic cracking operation. Hence, the hydroconverted product isfed directly to a fluid catalytic cracker operating on a cheap amorphouscatalyst at low oncethrough 430° F.- conversion (ca. 25%) but at high950° F.++ conversion (ca. 95%). The result is that a 97% yield (C₃ ⁺) ofa synthetic crude suitable for further processing in conventionalrefinery equipment is obtained. Coke yield, produced on the crackingcatalyst, is 7.5 wt.%.

By operating the reactor, or reactors, containing the R-1 catalyst at astart-of-run temperature of about 750° F. and at a space velocity ofabout 0.5 V/Hr./V, a product is made that is suitable for use in acatalytic cracker employing zeolite cracking catalyst. By operating atabout an 80% 430° F.- conversion, a C₃ ⁺ yield of 107 volume percent anda coke-on-catalyst yield of 7.5 wt.% can be obtained. However, thepreferred mode of operation is to remove 90% of the metals from the rawfeed with the R-1 catalyst at a SOR temperature of about 750° F. and ahigh space velocity of about 1.0 V/Hr./V. This product is now suitablefor R-2 service to provide feeds which can be used directly inconventional commercial petroleum operations, especially in conventionalhydrocracking and catalytic cracking operations for the production ofgasoline and other light distillates. The product from R-2 shouldcontain about 2 ppm heavy metals, or less, with a Con carbon of about3.3 wt.%. This material, when converted in a catalytic cracker employingzeolite catalyst at a catalyst makeup rate of 0.4 lb/Bbl. at about 80%430° F.- conversion, will produce a yield of 110 vol.% C₃ ⁺ and 6.7 wt.%coke on catalyst.

In the preferred mode of operation (i.e., 750° F. SOR and 1 V/Hr./V),this catalyst will have removed up to 90% and more of the metals in theraw feed after an operation of 27 or more days, the catalyst retainingover about 95% of its weight of metals from whole heavy crudes andresiduum feeds. The amount of sulfur and nitrogen that is removed iscomparable to that presented in the preceding paragraph.

In utilizing R-2 catalyst, in its most preferred form, the number ofpores ranging between about 100-200A absolute pore size diameter ismaximized, as is the surface area and pore volume consistent withpractical catalyst preparation procedures and with regard to the crushstrength requirements of the process. This means, of course, that thenumber of pores of diameter which are smaller than 100A (especially50A-) or greater than about 200A are minimized, especially the 300A+pores. R-2 catalyst of such character has thus proven outstanding in R-2service which, while not as stringent as R-1 service, is nonethelessrather severe, the R-2 catalyst retaining considerable quantities ofheavy metals while yet remaining active for Con. carbon conversion overlong periods. Moreover, the R-2 catalyst accomplishes this whileachieving high hydrodesulfurization and hydrodenitrogenation of thefeed. For example, operating at 650° F. SOR temperature and at a spacevelocity of 0.5 V/Hr./V, the R-2 catalyst reduces the metals content ofthe R-1 product from a level of about 60 ppm to about 5 ppm,representing about 99% metals removal based on total feed. At the sametime, asphaltenes are reduced to near 1 wt.% which is necessary forobtaining Con. carbon levels of 2-3 wt.%, based on product. Sulfur levelreaches about 0.3 wt.%, representing over 90% removal of sulfur based onthe raw feed. The catalyst is also effective for effecting 1050° F.+conversions, and conversion levels (based on raw feed) of 60% and higherhave been obtained. The product of R-2 service is suitable as feeds forconventional petroleum processing operations, particularly hydrocrackingand catalytic cracking operations.

The reasons for the effectiveness of the R-1 catalysts in thehydroconversion of the 1050° F.+ hydrocarbon portions of heavy crudesand residua, and the effectiveness of the R-2 catalyst in thehydroconversion of the 1050° F.+ hydrocarbon portion of the products ofR-1 service are not understood. However, whereas there is no desire tobe bound by any specific theory of mechanism, a theory has beenpostulated which aids in explaining some of the results which have beenobserved. It is thus believed that the pore sizes for R-1 and R-2catalysts are selectively adsorptive as regards asphaltenes which rangein size from relatively small to very large in terms of their molecularweight and physical size. The range of pores of about 100-275A diameterin the case of the R-1 catalyst are thus believed to admit asphaltenesof small and even relatively large sizes, with hydrogen, into contactwith a great number of reaction sites due to this penetration. The highnumber of reaction sites is thus drastically increased vis-a-visconventional catalysts because of the unusually high surface area andpore volume which provides essentially optimum hydroconversion of thesemolecules as they penetrate into the interior of the catalyst particles,and are caused to react by the conditions imposed thereon. This poresize range facilitates egress of the reacted moieties, or by-products ofthe reaction. On the other hand, pores of smaller diameter either do notpermit ingress of relatively large amounts of asphaltenes due to thevery large size, or the egress of the asphaltenes which are admittedinto the particles is hampered by the small size of the pores, or both.It is found that the diffusivity of asphaltenes into a catalystparticle, increases with increase in the pore diameter of the particle,and consequently the activity of the catalyst is effectively increaseddue to the greater availability of reactive sites. However, as porediameter is increased, the surface area of the catalyst particle isdecreased. One thus finds that, at constant intrinsic activity, theeffective activity of a catalyst increases as pore diameter is increaseddue to the increased diffusivity of the particle; and decreases due tothe decrease in surface area. The net effect, however, is that there isan optimum range of pore size distributions for catalyst of given, orconstant, average particle size. This optimum range of effectiveactivity is found to shift with change in particle size, in particles ofsimilar surface area, and pore volume, apparently because of the greaterdifficulty of asphaltene molecules to diffuse through the longerchannels of larger particles vis-a-vis the lesser difficulty ofasphaltene molecules to diffuse through the shorter channels of smallerparticles. The R-2 catalyst may behave in analogous manner, as regardsthe ingress of asphaltenes in their penetration into the depths of thecatalyst particle in their quest for active reaction sites. However, theeffect of particle size on the effective activity is far less apparentwith R-2 catalyst vis-a-vis R-1 catalyst. The pore size distribution ofthe R-2 catalyst, in combination with the high surface area and porevolume, however, does apparently optimize the activity and selectivityof the catalyst for R-2 service wherein the asphaltenes are of loweraverage molecular weight, a large number of the asphaltenes having beenreduced in size by conversion in R-1 service.

A tri site mechanism is postulated in the reaction of the asphaltenesafter their penetration into the catalyst particle. The asphaltenes, themolecular make-up of which can be generally characterized as layers offused benzene rings and associated appended alkyl groups, first contacta dissociative adsorption site such that the layers are separated onefrom another. This is believed a type of hydrogen intercalation orcracking reaction which occurs at the site of a Group VIB or Group VIIImetal or at active cracking sites, e.g., SiO.sub. 2 /Al.sub. 2 O₃ sites.The asphaltenes, thus reduced in size such that there is greaterexposure of the heavy metal atoms within the molecule (Ni, V, Fe, etc.),then contacts a metal abstraction site whereon the metal is removed fromthe asphaltene molecules. The metal abstraction sites are believedincreased by the Group IVA metal promoters, and may be located at ornear the site occupied by a Group IVA metal. The Group VIB or Group VIIImetal sites again act as "hydro-healing" sites, or locations whereinbonds dissociated by break-away of the metal from the molecule aresatisfied by addition of hydrogen to the molecule.

In a preferred method for the preparation of these novel catalysts,catalysts which at least meet the marginal requirements of R-1 and R-2catalysts as regards desired pore size distribution are prepared fromalumina in a synthesis reaction, as gels or cogels wherein certaincritical conditions must be observed as regards the concentration ofreactants in the synthesis solution, the acidity of the synthesissolution, and the temperature of the synthesis reaction. Gel preparationwithout added metals, of course, requires subsequent incorporation,e.g., impregnation, of metals whereas in cogel preparation the metalsare added at the time of gel formation. In such preparations, analuminum halide, e.g., aluminum chloride, is first dispersed or slurriedin water or alcohol in certain critical proportions, defined forconvenience in terms of the molar ratio of water (or alcohol):aluminumhalide dependent on whether it is desired to produce an R-1 or R-2catalyst. The temperature of the aluminum halide-water (or alcohol)slurry, to which the desired Group VIB and Group VIII metals, and othermetals, can be added as may be desired as in forming of a cogel, is thenlowered. Normally, water is used as the solvent, but alcohols such asmethanol can be used, though pore sizes tend towards the smallerdiameters with alcohol solvents. It is also essential in the reaction toadd a reagent which will remove the halide from solution whilemaintaining pH in the range of 5-8, this being preferably accomplishedby addition of an olefin oxide, e.g., ethylene oxide, propylene oxide,and the like, which forms a halohydrin. The reaction is necessarilycarried out at relatively low temperature, preferably from about 30° F.to about 100° F., and more preferably from about 32° F. to about 60° F.The olefin oxide is added in at least stoichiometric quantities inrelation to the amount of halide to be removed from the solution, andpreferably is added in molar excess to the solution. In the preparationof catalyst which at least meets the marginal pore size distributionrequired of R-1 catalyst, the molar ratio of olefin oxide:halide rangesfrom about 1.5:1 to about 2.0:1 and preferably from about 1.5:1 to about1.7:1, while the molar ratio of water (or alcohol):aluminum halide ismaintained within a range of from about 15:1 to about 30:1, andpreferably from about 18:1 to about 27:1. In the preparation of catalystwhich at least meets the marginal pore size distribution required of R-2catalyst, the molar ratio of olefin oxide:chloride ranges from about0.3:1 to about 1.5:1, and preferably from about 1.0:1 to about 1.2:1,while the molar ratio of water (or alcohol):aluminum halide ismaintained within a range of from about 22:1 to about 30:1, andpreferably from about 26:1 to about 28:1. Failure to remove most of thehalide, e.g., chloride, from the reaction results in a failure to obtainthe desired crystal growth, failure to obtain the required pore sizedistributions, or failure to produce a crystal sufficiently stable toretain such desired pore size distributions throughout subsequent stepsrequired in completing the formation of the catalyst. It is believedthat the required crystalline structure which shall ultimately beproduced from the sol is of a nature of boehmite, termed for convenience"pseudo-boehmite," and that excessive halide concentration and high pHadversely affect the proper formation of such aluminum oxy hydroxidecrystalline structure.

After completion of the reaction, the temperature of the gel is raisedto from about ambient to about 180° F. to form a sol. Preferably, thesol is formed at essentially ambient temperature, ranging generally fromabout 70° F. to about 80° F. and, on proper aging, pseudo-boehmite isproduced. It is essential to age the gel at such temperature for atleast about 6 hours, and preferably for about 24 hours to about 72 hourswhile the gel is in contact with its syneresis liquid. Lesser periods ofaging results in reducing the uniformity of pore sizes, andsignificantly longer periods, particularly periods in excess of 6 days,often produces bimodal distribution of the pores. Failure to properlyage the gel, while it is in contact with the syneresis liquid, alsoproduces a crystal structure which is not sufficiently stable to retainthe desired particle size distributions in the subsequent and necessarysteps of washing, drying and calcination.

It has been discovered that Group VIII noble metals and lanthanum andlanthanum series metals, or compounds thereof, are admirably suitable aspromoters for providing narrow pore size distributions and, inconjunction with control of the concentration of the reactants employedin the synthesis, the temperature, and particularly the acidity of thesynthesis solution, these promoters can be used to provide R-1 and R-2catalysts of optimum pore size distributions. Catalysts which meet eventhe preferred specifications of R-1 and R-2 catalysts can thus be madeby incorporation of small amounts of Group IIIB metals of Atomic Number57 and greater, and Group VIII noble metals, or both, or compounds orsalts thereof, within the solution during the synthesis. Exemplary ofthe former are such metals as lanthanum, and the rare earth metals ofthe lanthanum series such as cerium, praseodymium, neodymium,promethium, samarium, europium, gadolinium, terbium, dysprosium,holmium, erbium, thulium, ytterbium and lutetium. Exemplary of the GroupVIII noble metals are ruthenium, rhodium, palladium, osmium, iridium,and platinum, which metals are less preferred than the lanthanum seriesmetals because of their greater cost. Suitably, such metals, orcompounds thereof, are added to the solution, for preparation of R-1 andR-2 catalysts, in molar ratios of promoter metals:aluminum halideranging from about 0.001:1 to about 0.06:1, and preferably from about0.01:1 to about 0.03:1. The reason for the effectiveness of thesemetals, particularly the lanthanum metals, generally added as solublesalts, e.g., as halides, acetates, nitrates, sulfates, etc., inproducing the high uniformity of pore sizes in the desired ranges, whenemployed at the conditions defined, is not understood.

The syneresis liquid, after the aging step, is poured off of the gel orcogel. In the case of a gel, the gel can next be crushed to the desiredparticle size, air dried, then thoroughly washed. It is particularlypreferred to wash the gel or cogel with alcohol, to remove contaminants,after which the catalyst is air dried at room temperature, and thendried at mild temperatures, e.g., at about 175°-225° F. for about 3 to 6hours, then calcined, e.g., by heating at about 800°-1100° F. for about1 to 4 hours, and, the gel, then impregnated with a predetermined amountof the desired metal, or metals. The washing step is critical in theformation of the desired pore size distribution. Generally, isopropanolor one of the intermediate alcohols, e.g., n-propyl isobutyl and thelike promotes the formation of the desired pore sizes. Methanol, on theother hand, forms smaller pores generally, e.g., 0-100A, and hexylalcohol forms larger pores, e.g., 300+A. Mixtures of water andintermediate alcohols also favor the formation of 0-100A pores.

Impregnation of the alumina can be done prior or subsequent to thecalcination step. If subsequent to the calcination step, it is best toallow the calcined alumina to equilibrate with the moisture in the airfor 4-6 hours prior to impregnation to avoid damage to the porestructure. It is imperative that the impregnation be done with anon-aqueous solution, e.g., alcohol, rather than water solution. Ifwater solutions are used, the pore structure will readily shrink to the0-100A pore diameter range during subsequent drying and calcination. Thecatalytic metals, e.g., Co and Mo, are dissolved in alcohol, e.g.,methanol, and preferably isopropanol, and the solution imbibed into thealumina. Drying for 16-24 hours in air at ambient conditions, thendrying for about 3-6 hours at 175°-225° F., and then calcining at800°-1100° F. for 1-4 hours, will preserve the desired pore structure.The catalyst is then crushed and screened to the desired particle sizefor testing, usually 14-35 mesh (Tyler).

Extrudates of outstanding strength and quality, which meet therequirements of both R-1 and R-2 catalysts, can be prepared inaccordance with a preferred and novel method of this invention whichembodies extrusion of a gel or cogel of preselected pore sizedistributions falling within the R-1 and R-2 catalyst ranges, or whichcontains pores of size distribution sufficiently large that when the gelis subjected to extrusion at the required conditions the reduction inthe size of the pores caused by the extrusion and aging steps willreduce the pore sizes such as to cause them to fall within the R-1 andR-2 catalyst ranges. The gel or cogel, at the time of extrusion, is ofcritical liquids-solids content (generally produced by drying), it hasbeen previously aged within syneresis liquid for preselected periods atconditions involving critical time, temperature, or time-temperaturerelationships and, after extrusion, the extrudate is dried to provide acritical liquid-solids content and, in a preferred embodiment, thenreturned to syneresis liquid, without washing, and again aged forspecific critical periods at conditions involving critical time,temperature, or time-temperature relationships.

In the preparation of an extrudate, a gel or cogel is initially preparedfrom a sol, preferably one containing a Group VIII noble metal, ormetals, or lanthanum and lanthanum series metals, or admixtures thereof,in the range of proportions previously described, by varying the molarratios of water (or alcohol):aluminum halide and olefin oxide:halide,and also within the ranges described consistent with the requirements ofproducing an R-1 catalyst, if an R-1 catalyst is desired, or with therequirements of producing an R-2 catalyst, if an R-2 catalyst isdesired. Subsequent to formation of a gel or cogel of the requiredproperties, the gel or cogel is initially aged in syneresis liquid atcritical time, temperature, or time-temperature relationships sufficientto increase the crush strength of the finished particle and to providethe desired pore size distribution of the gel or cogel, or to preservesuch pore size distribution sufficiently that when subjected toextrusion and further aging at the required conditions the reduction insize of the pores caused by the extrusion will produce pore sizedistributions falling within the R-1 and R-2 catalyst ranges. This isaccomplished in part by the presence of the Group VIII noble metals orlanthanum series metals, or both, which inhibits or tends to inhibit thenormal tendency to reduce the sizes of the pores during the necessarystep, or steps, of aging. The crush strength is increased, and pore sizedistribution preserved by aging the gel or cogel prior to extrusion,preferably containing the Group VIII or lanthanum series metals, orboth, in syneresis liquid (1) for an initial time period ranging atleast 6 hours, and up to about 30 days, or longer, preferably for aperiod of from about 1 day to about 6 days, and more preferably fromabout 24 hours to about 72 hours, at generally ambient temperatures,i.e., about 50° F. to about 80° F., or by aging (2) at elevatedtemperatures ranging from about 80° F. to about 180° F., preferably fromabout 100° F. to about 160° F., or by aging (3) at a combination oftime-temperature relationships within these ranges of expressconditions. It is preferred, however, to subject the gel or cogel to aninitial aging for a rather short period, (a) preferably from about 1 to3 days or, more preferably, from about 24 hours to about 30 hours, atambient conditions, or (b) at higher temperatures ranging from about 80°F. to about 180° F., preferably 100° F. to about 160° F. for shorterperiods, preferably ranging from about 10 hour to about 24 hours, andmore preferably from about 15 hours to about 20 hours, and then toextrude, dry the extrudate to a critical liquid-solids content, andthereafter again subject the extrudate to a subsequent aging insyneresis liquid.

The gel or cogel, after the initial aging period, is separated from thesyneresis liquid and partially dried by standard techniques, e.g., asdescribed, to produce a gel or cogel containing from about 12 percent toabout 40 percent, and preferably from about 15 percent to about 25percent solids content, based on the total weight of the gel or cogelwith its occluded liquid. The gel or cogel is preferably crushed to lessthan 10 mesh (Tyler series) particle sizes and then extruded through adie to produce extrudates of desired diameter, and the extrudates arethen cut into desired lengths. Efforts, on the one hand, to extrude agel or cogel having too low a solids content generally proveunsuccessful or, if successful, the extrudates will be of poor qualityand may even deteriorate and crumble on subsequent aging in syneresisliquid. Extrusion of a gel of too high solids content adversely affectsthe pore size distribution previously developed in the gellation, thecrush strength and the larger pores generally being substantiallyreduced in size. After extrusion, and formation of the extrudate, theextrudate must again be dried to a solids content of >25 wt.%. If theextrudate is to be subsequently aged, as preferred, the extrudate, afterdrying, is then directly transferred, without washing, to the syneresisliquid. In the subsequent aging in syneresis liquid, the extrudate isagain treated at critical time, temperature, or time-temperaturerelationships to preserve the required R-1 and R-2 pore sizedistributions. Suitably, this is accomplished by aging the extrudate inthe syneresis liquid (1) for a period ranging at least 6 hours, and upto about 30 days, or longer, preferably for a period ranging from about1 day to about 6 days, and more preferably from about 24 to about 72hours at ambient conditions, or by aging (2) at elevated temperaturesranging from about 80° F. to about 180° F., preferably from about 100°F. to about 160° F., for periods ranging from about 10 hours to about 24hours, preferably from about 15 hours to about 20 hours, or by aging (3)at a combination of time-temperature relationships within these expressconditions. The extrudate is then again necessarily dried to provide asolids content of >25 wt.%, and then washed, preferably with alcohol.Failure to dry the gel to the required solids content can producedisintegration of the particles in washing. A gel or cogel properlyaged, properly dried to the required liquids-solids content, properlyextruded, without washing, and then again dried to the required solidscontent, the extrudate subsequently aged for the required period, andthen dried to the required solids content prior to washing will provideextrudates of superior strength and quality.

A low torque extruder, Model 0.810 Research Extruder manufactured byWelding Engineers of King of Prussia, Pennsylvania, has been found toproduce extrudates of outstanding quality when produced pursuant tothese specifications. Extrudates of superior crush strength can beformed in producing both R-1 and R-2 types of catalysts. After passagethrough a die to provide shapes of predetermined selected diameter,particularly for use in ebullating and fixed beds, the extrudates can becut in the desired lengths, dried to critical solids content, aged inthe syneresis liquid and again dried to control solids content, washed,preferably in alcohol as previously described, again dried, calcinedand, where desired, the so-formed extrudate then impregnated with thedesired metal, or metals, or with an additional metal, or metals.

The metals-containing catalyst, whether formed as a gel or cogel, canthen be contacted with hydrogen and hydrogen sulfide, or hydrogensulfide precursor, or both, in situ or ex situ, in a subsequent step, orsteps, to reduce and sulfide all or part of the metal salts and activatethe catalyst. The sulfiding is generally carried out by passing hydrogensulfide in admixture with hydrogen through a zone of contact with thecatalyst. The temperature of sulfiding is not especially critical, butis generally carried out in the range of about 500 to about 900° F.,preferably from about 600° F. to about 750° F. The time required for thesulfiding of the metals is generally short and not more than an hour, orat least no more than one to four hours is generally required tocomplete the sulfiding. Typically, in sulfiding the catalyst, thecatalyst is contacted with a dilute gaseous solution, e.g., about 5 toabout 15 percent, preferably from about 8 to about 12 percent, ofhydrogen sulfide in hydrogen, or hydrogen plus other nonreactive gases,and the contacting is continued until hydrogen sulfide is detected inthe effluent gas. Such treatment converts the metals on the catalyst tothe sulfide form. Sulfur-containing hydrocarbons, such as gas oils andthe like, may be used as hydrogen sulfide precursors.

In accordance with the present hydroconversion process, the R-1 catalystis contacted in a reaction zone with a hydrocarbon or hydrocarbonaceousfeed, e.g., a liquid derived from coal by hydrogenation, a heavy crudeor residua feed, in the presence of hydrogen, at conditions of severitysufficient to achieve the desired conversion of the 1050° F.+ materialsto lower molecular weight, or 1050° F.- materials, and simultaneously toremove at least about 80 weight percent, and preferably from about 85weight percent to about 90 weight percent of the heavy metals,particularly vanadium and nickel, from the feed. Removal of the heavymetals is enhanced by the combination of conditions, particularly thatof temperature, which enhances the conversion and results in somecleavage and reduction in the size of the asphaltenes, and the selectivepore size distribution of the R-1 catalyst, the 100-275A pore sizeopenings accepting asphaltenes ranging from small to relatively largesize, with regard to whether or not such molecules were originally ofsuch size or reduced in size by the conditions of reaction. The small torelatively large size asphaltenes readily diffuse, with hydrogen, intothe depths of the catalyst particles wherein hydroconversion reactionegressing from the particle, along with unreacted materials, as morehighly hydrogenated lower boiling products.

In conducting the reaction, the R-1 catalyst is generally employed inone or more stages of a reactor, or reactors, aligned in series (whichcan and usually does include one or more stand-by or swing reactors, asdesired). The R-1 catalyst, after being reduced and sulfided generallyin situ within the reactor, is operated under conditions, the majorvariables of which are tabulated for convenience, as follows:

    ______________________________________                                                       Operable  Preferred                                            ______________________________________                                        Temperature, ° F., E.I.T..sup.(1)                                      Start-of-Run     700         750                                              End-of-Run       850         800                                              Pressure, psi    2000-10,000 2000-5000                                        Hydrogen Rate, SCF/B                                                                           3000-20,000 3000-10,000                                      Space Velocity, LHSV                                                                           0.25-5.0    0.5-1.0                                          ______________________________________                                         .sup.(1) Equivalent Isothermal Temperature (E.I.T.)                      

The hydrocarbon or hydrocarbonaceous feed, i.e., coal liquid, heavycrude or residua, is rendered by R-1 service more suitable as a feed foruse in a coking process or a resid catalytic cracking process.Preferably, however, the product of R-1 service is rendered a suitablegrist for R-2 service, and thereby made suitable as a feed for use inconventional petroleum refining processes, especially as a feed for ahydrocracking or catalytic cracking operation. The R-2 catalyst, asheretofore suggested, is of pore size distribution selective of a rangeof asphaltene molecules smaller than those accepted within the pores ofthe R-1 catalyst. The asphaltenes in the R-1 product are generallysmaller than those of the raw feed and can quite readily diffuse intothe pores of the R-2 catalyst. The R-2 reactor is specifically designedto remove the remaining metals such that the product will contain <5 ppmmetals and <2-3 wt.% Con. carbon. Conditions are needed that favor thehydrogenation of the fused benzene rings of the asphaltene fragmentsfollowed by the cracking and dealkylation of the saturated rings. Inthis way, Con. carbon can be effectively reduced to the desired level.These conditions also favor the removal of the very refractory remainingmetals. Conditions favoring this type of reaction are low start-of-runtemperature, e.g., 650-700° F., at high hydrogen partial pressure, e.g.,2000-5000 psig.

In contrast to the R-1 catalyst, the R-2 catalyst removes less metalsand Con. carbon on an absolute basis but percentage-wise it removesabout the same amount of the metals. This is also true of the sulfur andnitrogen removal reactions. However, this catalyst is more effective onthe most refractory molecules and must be quite active to accomplishthis reaction, especially at the low temperature required.

The R-2 catalyst, which differs from R-1 catalyst, is effective in thehydroconversion of smaller molecules, far more so than an R-1 typecatalyst. Albeit it has pores maximized within a range of diameterssmaller than the R-1 catalyst, it does not encounter diffusion problemswith the conversion material produced in R-1 service. The smaller poresprevent the very large asphaltene molecules from entering the poreswhich severely diminish the much needed hydrogenation function of thecatalyst.

In R-2 service, the R-2 catalyst is generally employed in one or morestages of a reactor, or reactors aligned in series. The R-2 catalyst,after being reduced and sulfided generally in situ within the reactor,is operated under conditions, the major variables of which are tabulatedfor convenience as follows:

    ______________________________________                                                       Operable  Preferred                                            ______________________________________                                        Temperature, ° F., E.I.T.                                               Start-of-Run    600         650                                               End-of-Run      850         775                                              Pressure, psi    2000-10,000 2000-5000                                        Hydrogen Rate, SCF/B                                                                           3000-20,000 3000-10,000                                      Space Velocity, LHSV                                                                           0.25-5      0.25-2.0                                         ______________________________________                                    

The invention will be more fully understood by reference to thefollowing selected nonlimiting examples and comparative data whichillustrate its more salient features. All parts are given in terms ofweight units except as otherwise specified.

Examples 1-7, immediately following, describe preparation of a series ofR-1 and R-2 catalysts, inclusive of gels and cogels, wherein pore sizedistribution is controlled and set during gellation. Examples 1-4 thusdescribe the preparation of gel type catalysts under varying conditionswhich favor the formation of R-1 or R-2 catalysts, respectively.Catalysts A and B are thus R-1 pre-catalysts, and Catalysts E and F areR-2 pre-catalysts. Example 5 describes preparation of R-1 catalysts,prepared from cogels, including Group VIB and VIII metals. Examples 6-7describe preparation of vastly improved gel type catalysts of both theR-1 and R-2 types.

EXAMPLES 1-4

(preparation of Gel-Type Catalysts A, B, E and F)

In a first series of preparations, 1160 gram portions of AlCl.sub.3.sup.. 6H₂ O were weighed, transferred to large glass beakers, and thenslurried in portions of deionized water ranging from 15:1 to 27:1. Theseveral portions of slurried material were each then cooled to 35° F.,and gaseous ethylene oxide was then introduced at a rate of 12.5 gramsper minute until sufficient ethylene oxide had been added to providemolar ratios of C₂ H₄ O/HCl ranging from 1.1 to 1.6.

The resulting clear solutions were then allowed to slowly warm to anambient temperature of 75° F., a rigid gel having begun to form afterabout 1 hour. The gels were permitted to age at this temperature forperiods ranging 24 to 72 hours, each in contact with its own syneresisliquid, the syneresis liquid having become visible as a stratified layerabove the blocks of solidified gels and between the glass walls and sideboundaries of the solidified gels which shrink away from the glass andexude the syneresis liquid.

The gels, after the aging period, were each then separated from itsrespective syneresis liquid by merely pouring off the liquid. The gels,having the appearance of dry blocks of material, were then crushed intoparticulate masses, and each then thoroughly washed with 5 gallons ofisopropyl alcohol containing 1000 cc NH₄ OH in a column or by successivedecantation. The washing was continued in each instance until theeffluent from the column was free of chloride, as determined by testingfor chloride with silver nitrate test solution. The particulate masseswere then thoroughly dried in air for 15-25 hours and at 190° F. forperiods ranging between 6 and 24 hours, and thereafter calcined at 1000°F. for periods of from 2 to 4 hours.

The materials formed in these synthesis reactions, which were foundadmirably suitable as supports for use in the preparation of both R-1and R-2 catalysts, are characterized in Table I as R-1 Catalysts A and Band R-2 Catalysts E and F, respectively.

EXAMPLE 5

(preparation of Cogel-Type Catalysts D and D')

The foregoing procedure was repeated, except that in this instance twocogels were separately prepared, each according to the followingspecifics: 1160 grams of AlCl.sub. 3.sup.. 6H₂ O was slurried in 500 ccdeionized water and, after addition of one-half of the required amountof ethylene oxide, solutions were added which contained (a) 64.2 gramsof CoCl.sub. 2.sup.. 6H₂ O dissolved in 200 cc H₂ O and (b) 95 grams ofphosphomolybdic acid dissolved in 200 cc H₂ O. The balance of theethylene oxide was then added. The final preparation of a catalyst,which contained 6 wt.% CoO and 20.5 wt.% MoO.sub. 3, was then completed,these catalysts being identified as Catalysts D and D' in Table I.

EXAMPLES 6-7

(preparation of Improved Gel-Type Catalysts C and G)

Examples 1-4 were again repeated except that in this instance 1.0 wt.%rhodium or 3.5 wt.% lanthanum was slurried with the AlCl₃. 6H₂ O inpreparation of the sol. The catalysts formed in this manner areidentified in Table I as Catalysts C and G, respectively.

The data presented by reference to Table I thus show that catalysts,having only a marginal amount of pore sizes in diameters less than 50A,i.e., 50A-, and with a large amount, preferably a maximum of pore sizesin diameters ranging 150-250A can be prepared by maintaining molarratios water:aluminum chloride of about 15 to 30, preferably 18 to 27;molar ratios ethylene oxide:HCl of about 1.5 to 2, preferably 1.5 to1.7; and by aging the catalysts for periods ranging from about 1 to 3days, preferably from 1 to 2 days. In preparing catalysts with smallerpores, these data show that such catalyst can be also prepared with aminimum of pore sizes of diameter within the 50A- and 300A+ ranges, andwith a maximum of pore sizes of diameter ranging from about 100A to200A. This is accomplished by maintaining a molar ratio ofwater:aluminum halide ranging about 22 to 30, preferably 26 to 28; amolar ratio of ethylene oxide:HCl of about 0.3 to 1.5, preferably 1 to1.2; and by aging the catalyst for periods ranging about 1 to 3 days,preferably 1 to 2 days. This limited aging improves the uniformity ofpore size distributions with the desired ranges, as relates to thepreparation of gels and cogels. The use of trace metals such as GroupVIII noble metals or lanthanum and lanthanum series metals is also foundto increase the uniformity and maximization of the desirable pore sizedistributions. Moreover, catalysts having very large pores can beprepared having a minimum of pore sizes ranging 50A- and 350A+, and witha large amount, preferably a maximum of pore sizes of diameter ranging175-275A suitably by preparation of a cogel as described, e.g., inExample 5, with subsequent extrusion of a particulate mass of the cogelto provide an extrudate. Extrusion of cogel of Example 5 can thus beemployed to provide extrudates of 1/16 inch particle size diameterhaving the properties, e.g., of Catalyst XX as described by reference toTable IV, Examples 10-17.

Once the gel is set by observing conditions which favor the desiredranges of pore size distributions, it is also important to wash the gelsufficiently to remove essentially all traces of halides and syneresisliquid. Failure to accomplish this removal will result in a loss of thedeveloped pore size distributions. An alcohol wash has been foundparticularly effective in such capacity, the C₂ to C₆ alcohols,particularly the C₃ or isopropyl alcohol, having been found particularlyeffective in preserving the developed pore size distribution throughoutthe subsequent steps required in completing the preparation of thecatalysts.

The actual water content of the alcohol used in the wash was found tohave a profound effect on the pore size distributions, the surface areasand pore volumes of the catalysts, and on subsequent drying it was foundthat these properties vary dependent on the amount of water, if any,contained in the alcohol wash. As with the syneresis liquid, if the washalcohol contains water, the pore volume shrinks with only minorattendant reduction in surface area. The result is a reduction in theaverage size of the pores. Thus, because water decreases pore sizedistribution and pore volume, it is generally preferred to use anhydrousalcohol for catalyst preparations. The following examples demonstratethe effect of water on these properties, especially on pore volume andpore size distributions in the alcohol washing and drying sequence.

                                      TABLE I                                     __________________________________________________________________________    Catalyst     A      B      C.sup.(1)                                                                            D.sup.(3)                                                                         D'  E      F      G.sup.(2)             __________________________________________________________________________    Type         Al.sub.2 O.sub.3 -gel                                                                Al.sub.2 O.sub.3 -gel                                                                Improved                                                                             Cogel                                                                             Cogel                                                                             Al.sub.2 O.sub.3 -gel                                                                Al.sub.2 O.sub.3                                                                     Improved                                         Al.sub.2 O.sub.3 -gel        Al.sub.2 O.sub.3                                                              -gel                  H.sub.2 O/AlCl.sub.3, Mol/Mol                                                              27     18     15     15  15  27     27     28                    C.sub.2 H.sub.4 O/HCl, Mol/Mol                                                             1.6    1.6    1.6    1.6 1.6 1.1    1.1    1.4                   Age, Days    1      1      3      1   1   1      2      1                     Surface Area, m.sup.2 /gm.sup.(4)                                                          352    339    325    330 373 270    313    373                   Pore Volume, cc/gm.sup.(4)                                                                 1.77   1.76   1.85   1.23                                                                              1.5 0.81   1.10   1.23                  Pore Volume Distribution,                                                     % in 50A-    --     --     --     1.5 --                                          50-150A  --     0.6    --     15.5                                                                              26.0                                        150-250A 25.0   18.7   40.2   44.1                                                                              47.1                                         250-350A                                                                              69.5   55.4   59.8   33.0                                                                              20.1                                        350A+    5.5    25.3   --     5.9 6.8                                     % in 50A-                                 --     --     --                        50-100A                               19.7   1.0    6.3                       100-200A                              78.1   87.7   91.5                      200-300A                              2.2    6.8    1.6                       300A+                                 --     4.5    0.6                   __________________________________________________________________________     .sup.(1) Contains 1% Rh added during gellation.                               .sup.(2) Contains 3.5% La.sub.2 O.sub.3 added during gellation.               .sup.(3) Contains 6% CoO, 20.5% MoO.sub.3, 1% P.sub.2 O.sub.5.                .sup.(4) Surface area measurements are B.E.T. areas measured by nitrogen      adsorption at the boiling point of nitrogen using a standard single point     determination at a nitrogen pressure of 160 mm Hg in which the term C in      the B.E.T. equation is assumed to be constant and equal to 70. Errors         introduced into the surface area measurement by the assumption of C = 70      generally do not exceed 5% over that obtained from the rigorous               multi-point measurement. Pore volumes are total pore volumes measured at      the saturation pressure of boiling liquid nitrogen.                      

EXAMPLE 8

A series of gel type catalysts (H, I, J, K, L) was prepared, thepreparation steps employed and the composition of these catalysts beingsimilar to that previously described with regard to Catalyst B, exceptthat these catalysts were aged somewhat longer during the period ofgellation. In the preparation of these catalysts, except as regardsCatalyst H, however, water in varying concentrations was added to theisopropyl alcohol used as a wash. The results of these runs aretabulated as follows:

                  TABLE II                                                        ______________________________________                                        Catalyst     H       I       J     K     L                                    ______________________________________                                        H.sub.2 O in Alcohol                                                                        0      2.5      5     10    25                                  (Vol. %)                                                                      Surface Area, m.sup.2 /gm                                                                  382     393     398   373   354                                  Pore Volume, cc/gm                                                                         2.07    1.93    1.82  1.59  0.92                                 Avg. Diameter, A                                                              (4 PV/SA × 10.sup.4)                                                                 217     197     183   112   104                                  ______________________________________                                    

These data thus show that, with isopropyl alcohol, pore volume isdecreased as the water content of the alcohol increases from 2.5 to 25percent (vol.) with only nominal change in the surface area. The resultis to decrease the average size of the pores.

The presence of water is also found to decrease the pore volume and poresize distributions during the impregnation steps, wherein thehydrogenation-dehydrogenation and other catalytic components are addedto alumina supports. For best results, it has been found desirable toadd the metals by impregnation of the supports with nonaqueous solutionsof the metal salts, preferably alcohol solutions. Water, however, shouldnot be used. The presence of water has been found to decrease both porevolume and pore size distribution drastically. It is thus believed thatwater enters the pores, redissolves and, during drying, some of theredistributed alumina forms deposits within the pores. Thus, someshrinkage of the previously developed pore sizes results from the use ofwater during the impregnation step and hence its use is preferablyavoided. The following example thus presents data showing preparation ofa cobalt-molybdenum on alumina catalyst by impregnation of a suitablealumina support with a metals-containing methanol solution. Comparisonis made between the surface area, pore volume and pore size distributionof the catalyst and the unimpregnated support from which the finishedcatalyst was made.

EXAMPLE 9

Alumina prepared pursuant to the procedure used in preparation ofCatalyst E was split into two portions, one, a precatalyst or support,termed for convenience Catalyst O, and a second 100-gram portion, termedCatalyst P, which was impregnated with a solution containing 32.4 gramsof CoC1₂. 6H₂ O and 47.6 grams of phosphomolybdic acid dissolved in 162cc of methanol. Catalyst P was subsequently dried at room temperatureand at 190° F. and then calcined for 2 hours at 1000° F. The twocatalysts are compared in Table III, as follows:

                  TABLE III                                                       ______________________________________                                        Catalyst             0         P                                              ______________________________________                                        Wt.% CoO             --        6                                              Wt.% MoO.sub.3       --        20.5                                           Wt.% P.sub.2 O.sub.5 --        1                                              Surface Area, m.sup.2 /gm                                                                          336       246                                            Pore Volume, cc/gm   0.99      0.61                                           Pore Volume, Distribution,                                                    % in 50A-Pores       --        3.7                                                50-150A Pores    95.3      59.4                                               .150-250A Pores  4.7       31.9                                               250-350A Pores   --        4.7                                                 350A+ Pores     --        0.3                                            ______________________________________                                    

These data thus show that considerable pore volume shrinkage occurred,particularly in the 50-150A pore diameter ranges even as a result ofusing alcohol. This shrinkage must be compensated for by forming in thegel or cogel pores of larger pore size distribution than ultimatelydesired realizing that the shrinkage shall constitute a compensatingfactor. The shrinkage can be further minimized by using C₂ to C₆alcohols, preferably isopropyl alcohol, as the solvent.

The following examples and demonstrations describe preparation of aseries of extrudates from cogels (and gels), and define certain criticalfeatures required to obtain extrudates of good quality meeting therequirements of R-1 and R-2 catalysts. The technique of making catalystsin the form of extrudates is particularly applicable to the formation ofcatalysts in the 1/50-1/25 and 1/25-1/8 inch particle size ranges, andsphere forming techniques, particularly as described hereinafter, areparticularly applicable to the formation of catalysts in the 1/500-1/50inch particle size ranges. In making catalysts with the desired narrowpore size distributions, as shown, it is necessary to limit the time ofaging because aging produces shrinkage of pore size but, on the otherhand, aging is essential if extrudates of good strength are to be made,particularly extrudates of high crush strength, especially crushstrength in excess of 7 pounds. High crush strength is desirable, ornecessary, in certain types of processes. Thus, techniques are describedwhich have been found to speed up the aging process and to counteractthe effect of aging which tends to decrease the pore sizes of thecatalysts. The aging process can thus be carried out by (1) contact ofthe gel or cogel with syneresis liquid at ambient conditions for periodsranging to about 30 days, and longer; (2) contact of the extrudate, orpelletized form of the gel or cogel, for periods ranging to about 30days, or longer, in the syneresis liquid; (3) contact of the gel orcogel in syneresis liquid in an initial step prior to contact of theextrudate, or pelletized form of the gel or cogel, in syneresis liquid,as described in (1) and (2), which is preferred; (4) by high temperaturecontact of the gel or extrudate (or pelletized form of the gel orcogel), or both, by (5) a combination of these steps; and (6) Group VIIInoble metals, or lanthanum and rare earth metals of the lanthanumseries, are preferably included in the gellation step to counteract thepore shrinkage effect of aging on pore size distribution. In these data,it will also be observed that (7) critical solids contents are requiredprior to or subsequent to certain steps to avoid deterioration orweakening of the gel or extrudate. These include: (a) drying to about12-40 wt.% solids prior to extrusion or pelletizing of the gel or cogel,(b) drying to 25+ wt.% solids prior to the aging of extrudates, orpelletized gel or cogel, in syneresis liquid, and (c) again drying to25+ wt.% solids prior to alcohol washing.

EXAMPLES 10-17

Portions of gel, or cogel, comprising metals and alumina, were eachprepared by raising the temperature of sols prepared by reaction betweenaqueous slurries of aluminum chloride and ethylene oxide as describedfor the initial preparation of Catalysts D and D' (Example 5). Theportions of cogel were each used to prepare a series of catalystsdefined in Table IV below, referred to as Catalysts AA, BB, CC, DD, EE,FF (a gel), GG (a gel), XX and YY.

The portions of cogel (or gel) were each aged at 75° F. (Except CatalystEE which was aged at 160° F.), prior to extrusion, in its own syneresisliquid for periods ranging from 24 hours (1 day) to 30+ days. Theportions of cogel (or gel) were then dried in air for a time sufficientto provide twenty percent solids content, based on the total weight ofthe gel. In these cases, to prepare Catalysts GG, XX, and YY, the agedgel (or cogel) was crushed to <10 mesh particle size before extrusion.After extrusion in a Model 0.810 Research Extruder manufactured byWelding Engineers of King of Prussia, Pa., using a 1/16 or 1/32-inchdie, some of the extrudates were then further dried in air for a timesufficient to provide a twenty-five percent solids content, based on thetotal weight of the cogel (or gel). Some of the extrudates were thenreturned, without washing, to the syneresis liquid from which they wereoriginally removed, immersed therein and aged at 75° F. for one day. Theextrudates were again dried in air to 25 wt.% solids content, thensubsequently washed in isopropyl alcohol, oven dried in air at 190° F.,and finally calcined at 1000° F.

These several portions of gel or cogel, the manner in which each wastreated, and the properties of the series of catalysts, i.e., CatalystsAA, BB, CC, DD, EE, FF, GG, XX, and YY, produced therefrom,respectively, are referred to in Table IV below. The table shows, in thefirst two rows of figures, the number of days that each of the catalystswas aged in syneresis liquid prior to extrusion, and the number of days,if any, that each of the extrudates was aged in syneresis liquidsubsequent to extrusion. The next two rows of figures indicate,respectively, the solids content of the cogel (and gel) beforeextrusion, and subsequent to extrusion. The next row of figures, alsogiven under "Extrusion Conditions" gives, respectively, the percentsolids of the cogel (and gel) prior to the alcohol wash. Isopropylalcohol was used as the wash liquid in each case. The last seven rows ofFigures give the properties of the several extrudates. The porediameter, for convenience, is also listed in terms of average pore sizeas calculated by the conventional formula 4 × 10⁴ times pore volumedivided by surface area. For the 1/16 inch extrudate, 175-275A pores aregiven where for 1/32 inch extrudates 150-250A pores are given. Asdiscussed later, these are the important ranges for the particle sizes.

                                      TABLE IV                                    __________________________________________________________________________    Catalyst       AA   BB   CC   DD   EE   FF   GG   XX   YY                     __________________________________________________________________________    Size, Inches   1/16                                    1/32                   Age, Days                                                                      Before Extrusion                                                                            1    3    30+  1    1.sup.(1)                                                                          1.sup.(2)                                                                          1.sup.(3)                                                                          1    1                       Extrudates in                                                                  Syneresis Liquid                                                              after Extrusion                                                                            0    0    0    1    1    1    1    1    1                      Extrusion Conditions                                                           % Solids before                                                               Extrusion     20   20   20   20   20   20   20   20   20                      % Solids before                                                               Aging in Syn. Liq.                                                                          --   --   --   25   25   25   25   25   25                      % Solids before                                                               Isopropyl Wash                                                                              25   25   25   25   25   25   25   25   25                     Wash Liquid    Isopropyl Alcohol                                              Properties                                                                     Surface Area, m.sup.2 /gm                                                                   437  390  325  395  297  302  332  392  389                     Pore Volume, cc/gm                                                                          1.94 1.76 0.83 1.88 0.92 1.09 1.10 1.81 1.52                    Diameter, A                                                                    (4 PV/SA × 10.sup.4)                                                                 178  181  102  189  124  144  133  185  156                     Pore Size Distribution,                                                       % Pore Volume in                                                               0-50A        4.5  --   18.3 19.2 8.1  8.9  7.0  2.3  0.0                      175-275A     23.3 --   16.4 17.2 24.2 22.4 23.9 32.3 29.8                                                                          (150-250A)               350A+        31.9 --   23.0 21.3 21.7 25.6 20.7 21.6 24.4                    Strength, lbs.                                                                              1.3  +.2  10.7 3.7  14.0 4.6  8.1  4.4  3.7                    __________________________________________________________________________     .sup.(1) Extrudate aged at 160° F.                                     .sup.(2) Prepared from a gel containing 3.5 percent lanthanum (as the         oxide). Later impregnated with CoCl.sub.2.6H.sub.2 O and phosphomolybdic      acid and in amount sufficient to provide 6 wt.% CoO and 20.5 wt.%             MoO.sub.3.                                                                    .sup.(3) Prepared from a gel. The aged gel was crushed to <10 mesh            particle size before extrusion, and later impregnated with                    CoCl.sub.2.6H.sub.2 O and phosphomolybdic acid in amount sufficient to        provide 6 wt.% CoO and 20.5 wt.% MoO.sub.3.                              

These data show that Catalyst AA possesses a reasonably good pore sizedistribution in that it has low pore volume in the 0-50A pores and 350A+pores and reasonably good pore volume in 175-275A pores. It also hasgood surface area and pore volume. Unfortunately, it has low strength,i.e., 1.3 lbs., but by allowing the cogel to age for 3 days prior toextrusion (Catalyst BB), the strength can be markedly improved to 4.2lbs. Catalyst CC demonstrates the shrinkage of pores when cogel is aged30+ days prior to extrusion. The strength is excellent at 10.7 lbs. butthe low pore volume (0.83 cc/g) and excessive pores in the 0-50A confirman excessive shrinkage due to long term aging. Catalyst DD shows that byaging the extrudates in the syneresis liquid, a catalyst with fairstrength is formed (3.7 lbs.). In this case, however, the 0-50A poreswere excessive due to poor temperature control during the sol formingstep. It is important to control the sol forming temperature at 40°-50°F. to minimize these pores. As shown by Catalyst XX, a good extrudate isformed (4.4 lbs.) by good sol temperature control and aging of theextrudates in syneresis liquid. This catalyst had low pore volume in0-50A and 350A+ pores and high pore volume in 175-275A pores.

Further improvements in strength can be obtained by aging the gel (orcogel) at high temperature for short times as with Catalyst EE. By agingat 160° F., a catalyst with 14 lbs. crush strength was formed. However,excessive pore volume shrinkage occurred resulting in excessive porevolume in the 0-50A pores and a low total pore volume (0.92 cc/gm).

Catalysts can also be prepared by first extruding a gel followed byimpregnation of that extrudate with catalyst metals. This isdemonstrated by Catalysts FF and GG. These data are for the gels priorto impregnation. Good strength was obtained (4-8 lbs.) but pore volumeshrinkage occurred. Pore volume in 0-50A range is not unduly excessive,however.

One example of a 1/32-inch catalyst is given (Catalyst YY). Strength isbelow that desired (3.7 lbs.) but for 1/32-inch extrudates it has a goodpore size distribution with minimum 0-50A pores and 350A+ pores and alarge amount of pore volume is 150-250A pores which are best for1/32-inch particles.

Spheres are the preferred forms of catalysts for use in ebullating bedsand slurry reactors (reaction zones), the size thereof ranging about1/50 inch particle size diameter, and smaller. Spheres, of course, canbe utilized in a fixed bed (e.g., in particle size diameter rangingabout 1/32-1/8 inch), but most often are utilized in ebullating bed andslurry reactors where particle size diameters most often range1/32-1/250 inch, and smaller. A very effective range for spheres inebullating and slurry reactors is from about 100 to about 500 microndiameters. There are several known techniques for forming spheres, towit: (1) prilling, (2) gelling in a column, (3) centrifugal force, (4)gelling in a stirred vessel, or tank, and the like. In the preferredstirred tank method, a sol (gel or cogel) is heated and aged, whileagitated, in a mineral oil bath generally at temperatures ranging fromabout 75° F. to about 150° F., preferably from about 100° F. to about125° F. The amount of mineral oil:sol, on a volume basis, rangesgenerally from about 5:1 to about 20:1, preferably from about 8:1 toabout 12:1. The amount of agitation of the bath, and the height anddiameter of the tank, is selected to provide particles of desired size.Such technique is described in greater detail in Examples 18-20, below.

EXAMPLES 18-20

Portions of cogel, which contain metals and alumina, or portions of gelwhich contain alumina, were each prepared first by forming a sol asdisclosed in the preparation of Catalysts D and D' (Example 5), and thesols were then added to a stirred vessel containing mineral oil.

The preparation of the sols was as described by reference to Examples1-5, the slurried material formed by reaction between the aluminum saltand ethylene oxide having been removed from the beakers at temperaturesof about 35° F., and the temperature adjusted to about 55°-65° F. over aperiod of one-quarter hour prior to introduction of the portion of solinto the vessel containing the mineral oil. The sol was added slowly,i.e., at a rate of about 5-75 cc/min., over a period of one-quarter hourto avoid gelling prior to the introduction.

The amount of mineral oil:sol, on a volume basis, was maintained at10:1, and the temperature was maintained at 100°-150° F. Turbine typeagitators using various blade designs were employed, the size of theparticles produced being controlled by blade design, vessel design, andthe speed of revolution (revolutions per minute, RPM) of the blade.

For the formation of relatively small particles (e.g., 100-200 microns)a single blade turbine operated at 250 RPM proved best. For largerparticles (e.g., 300-400 microns), a six blade turbine at 75 RPM provedbest. The design of the vessel is critical. It was found that the ratioof the height of the vessel (H) to its diameter (D), i.e., H/D, shouldrange between about 1:5-1:2, preferably 1:4 to 1:3. The design of theturbine should be such that the impeller abuts the walls and bottom ofthe vessel. The ratio of the height of the impeller (H_(I)) to theheight of the vessel, H_(I) /H, should range from about 1:2 to about4:5, preferably from about 2:3 to about 3:4.

It is found that as the sol is added to the mineral oil, small spheresform in the oil. After completion of sol addition, the agitator isallowed to continue agitating for at least 30 minutes, preferably for aperiod ranging up to 2 hours. During this time, the spheres are gelled.The spheres are next separated from the oil, and the solids particleseither spread out over a solid surface to age, or surface washed toremove the mineral oil to avoid agglomeration of the solids particles.Suitably, the spheres can be surface washed with varsol or isopropylalcohol, or both, to avoid agglomeration, but care must be taken toavoid removal of syneresis liquid from the pores as opposed to mereremoval of the surface oil. The spheres are aged for about 1 day. Afterthis, the spheres are washed in isopropyl alcohol, with or without addedammonia, oven dried at 190° F., and then calcined at 1000° F. for 4hours.

Catalysts UU, VV and WW, so produced, are characterized as having thefollowing properties:

                  TABLE V                                                         ______________________________________                                        Catalyst          UU.sup.(a)                                                                             VV.sup.(b)                                                                             WW.sup.(c)                                ______________________________________                                        Vol. of Mineral Oil, cc                                                                         1000     10,000   10,000                                    Vol. of sol, cc   100      1000     1000                                      Mixing                                                                         Turbine          1 Blade  6 Blades 6 Blades                                   RPM              250      100      100                                       Gellation Temp., ° F.                                                                    150      100      120                                       Catalyst Properties                                                            Surface Area, m.sup.2 /g                                                                       278      244      330                                        Pore Volume, cc/g                                                                              0.54     0.49     1.15                                       Avg. Pore Dia., A                                                                               85       80      139                                        Pore Size Dist., % PV in                                                       0-50A           --       --       1.9                                         100-200A        --       --       33.8                                        300A+           --       --       21.0                                       Particle Size, microns                                                                         100-200  100-500  100-300                                   ______________________________________                                         .sup.(a) No rinse/No NH.sub.3 in wash.                                        .sup.(b) Rinse, no NH.sub.3 in wash.                                          .sup.(c) No rinse, NH.sub.3 in wash.                                     

Catalyst UU was formed in quantity with a 1-blade turbine at high RPM(250) and high temperature (150° F.). The particles were small due tohigh RPM and impeller design. The low surface area and pore volume aredue to high gella ion temperature (150° F.) and the fact that NH₃ wasexcluded from the isopropyl wash. Catalyst VV was made in a largervessel with a 6-blade impeller operated at 100 RPM and 100° F. Thecatalyst spheres were rinsed with varsol and isopropanol in this case toavoid agglomeration, and no ammonia was included in the wash. Due to thelower RPM and impeller design, particle size was increased to 100-500microns. Due to the improper rinse (i.e., varsol and isopropanolpretreated spheres prior to aging) and the lack of NH₃ in the wash, thesurface area and pore volume are lower than desired. Catalyst WWrepresents an excellent spherical catalyst prepared by this technique.By forming the spheres in the larger vessel using the 6-blade turbine at100 RPM and 120° F., spheres ranging in size from 100-300 microns weremade. Further, by carefully handling the spheres before aging to avoidagglomeration without the use of varsol and isopropanol rinse, theresulting spheres possessed good surface area and pore volume. Inaddition, 50A pores and 300A+ pores were minimized while maximizing100-200A pores which are highly desirable for particles in this sizerange. By decreasing the RPM to 75, particle size is further increasedto 300-400 microns.

EXAMPLE 21

Runs were conducted with each of Catalyst D, Q and R, of 1/32 inchaverage particle size, by contact with Cold Lake and Jobo Crudes,respectively, in a reactor which contained the catalysts as fixed beds.The runs were each conducted at two different temperature levels, atapproximately the same pressure level of 2250 psig, at two differentflow velocities and at hydrogen rates varying between 5500-8500 SCF/B.The following Table VIII shows the product inspections at the end of twodifferent time periods, the conditions of reaction being given at thetime the products were withdrawn for analysis.

Shown immediately below in Table VI are the analyses for Cold Lake andJobo crudes. In addition, the catalyst inspections for Catalysts Q and Rare given in Table VII. Catalyst Q is a commercially availablehydrodesulfurization catalyst having most of its pore volume in the0-100A region. Catalyst R was made in a manner similar to Catalyst D butwith longer aging of the gel.

                                      TABLE VI                                    __________________________________________________________________________    FEED ANALYSES                                                                            Cold Lake Crude                                                                         Jobo Crude                                                                           Kuwait Resid.                                     __________________________________________________________________________    Gravity, ° API                                                                    11.1      8.5    16.5                                              Sulfur, Wt.%                                                                             4.5       3.8    3.6                                               Carbon, Wt.%                                                                             83.99     83.92  84.64                                             Hydrogen, Wt.%                                                                           10.51     10.49  11.41                                             Con Carbon, Wt.%                                                                         12.0      13.8   9.0                                               Asphaltenes, Wt.%                                                                        17.9      17.7   --                                                Nitrogen, Wt.%                                                                           0.46      0.68   0.22                                              Metals, ppm                                                                    Ni        74        97     12                                                 V         180       459    58                                                Distillation, 1mm                                                              IBP, ° F.                                                                        463       518    451                                                5% (Vol.) 565       627    577                                                10        622       682    648                                                20        712       798    737                                                30        817       895    805                                                40        916       978    865                                                50        1019      1037   937                                                % Recovered                                                                             56.4      50.8   64.0                                               % Residue 42.4      48.2   36.0                                               FBP, ° F.                                                                        1047      1047   1047                                              __________________________________________________________________________

                  TABLE VII                                                       ______________________________________                                        CATALYST INSPECTIONS                                                          Catalyst             R         Q                                              ______________________________________                                        Surface Area, m.sup.2 /g                                                                           362       260                                            Pore Volume, cc/g    1.79       0.50                                          Pore Volume Distribution,                                                     % Pore Volume in                                                               0-50A Pores          1.4      11.1                                            50-150A             10.9      79.5                                            150-250A            17.6      6.1                                             250-350A            23.4      1.8                                             350A+               46.7      1.5                                            % CoO                 6        3.5                                            % MoO.sub.3           20       12.0                                           ______________________________________                                    

                                      TABLE VIII                                  __________________________________________________________________________                   Cold Lake               Jobo                                                  Catalyst R  Catalyst Q  Catalyst D  Catalyst                   __________________________________________________________________________                                                       Q                          Temperature, ° F.                                                                     651   751   651   751   600   750   600   750                  Space Velocity, V/Hr./V                                                                      0.91  1.0   0.91  1.0   0.95  1.1   0.95  1.1                  Time on Oil, Hrs.                                                                            277   1291  277   1291  66    270   66    270                  Product Inspections                                                            Gravity, ° API                                                                       13.0  18.8  14.2  16.7  11.2  18.3  11.2  16.8                  Sulfur, Wt.%  2.92  0.99  2.72  2.37  2.85  0.81  2.70  1.60                  Nitrogen, Wt.%                                                                              0.442 0.353 0.414 0.360 0.620 0.467 0.650 0.474                 Con. Carbon, Wt.%                                                                           10.7  6.25  10.29 9.70  11.53 6.73  12.54 10.18                 Asphaltenes, Wt.%                                                                           11.6  4.65  15.26 12.19 14.91 3.36  18.16 11.72                 Metals, ppm                                                                    Ni           40.1  14.6  56.9  41.8  75.1  18.3  92.0  70.9                   V            91.4  16.0  156.5 94.1  338.1 46.6  40.72 316.9                 1050° F. Conversion, Wt.%                                                            --    29    --    17    --    --    --    --                    1050° F.+ Quality                                                       Sulfur, Wt.%                               1.42         3.56                  Con. Carbon, Wt.%                          17.3        25.55                __________________________________________________________________________

These data thus show that Catalyst Q, the commercialhydrodesulfurization catalyst, is completely unsuitable for thetreatment of these heavy crudes at hydroconversion conditions, althoughCatalysts D and, to a lesser extent, Catalyst R are well suited for suchpurpose. Whereas Catalyst Q does effectively hydrodesulfurize the crudein some cases, the data clearly show that it is entirely unsuitable forremoval of heavy metals, for the reduction of Con. carbon, and for theconversion of asphaltenes.

In other comparative runs, for purposes of demonstration, Kuwaitresidua, a more conventional crude characterized as a light Arabianfeedstock, the inspections on which are given in Column 4 of Table V,above, Catalyst Q and Catalyst D were compared at similar but varyingconditions in hydrodesulfurization reactions with the results describedin Table IX, below.

                  TABLE IX                                                        ______________________________________                                        Temperature, ° F.                                                                            650-750° F.                                      Pressure, psig        2000                                                    Hydrogen Rate, SCF/Bbl.                                                                             4000                                                                 Catalyst Q                                                                            Catalyst D                                               Days on Oil    26                26                                           Average Temperature, ° F.                                                             710               710                                          Space Velocity, V/Hr./V                                                                      0.4       0.6     0.4   0.2                                    Product Inspections                                                            Gravity, ° API                                                                       24.8      22.7    23.6  24.1                                    Sulfur, Wt.%  0.25      0.64    0.45  0.28                                    Nickel, ppm   5.3       2.7     1.1   0.2                                     Vanadium, ppm 12.5      5.4     2.3   1.7                                     Nitrogen, Wt.%                                                                              0.09      0.17    0.16  0.14                                   ______________________________________                                    

These data show that Catalyst Q is better for desulfurization (anddenitrogenation) of a light feedstock than Catalyst D which is lesssatisfactory. However, the catalyst of the invention (Catalyst D) issuperior in metals removal even for this light feed.

EXAMPLE 22

Diffusion plays a very important role in the conversion of asphaltenesand removal of nickel and vanadium from heavy crudes. This is due to thelarger size of the diffusing molecules. Since sulfur is found in smallermolecules, the sulfur removal reaction is much less restricted bydiffusion. This is demonstrated in the following example. A catalyst wasprepared in a manner similar to that used in the preparation of CatalystD. This catalyst is designated Catalyst AAA. Properties of this catalystare given in the table below:

    ______________________________________                                        CATALYST AAA                                                                  Surface Area, m.sup.2 /g 366                                                  Pore Volume, cc/g        1.33                                                 Pore Volume Distribution, %                                                           0-50A Pores      4.3                                                          50-100A          10.0                                                         100-150A         13.3                                                         150-175A         5.2                                                          175-200A         6.5                                                          200-250A         13.4                                                         250-275A         6.3                                                          275-300A         6.9                                                          300-350A         9.7                                                          350A+            24.7                                                         % CoO            6                                                            % MoO.sub.3      20                                                   ______________________________________                                    

This catalyst was divided into three parts, each crushed, and sized toprovide particles having average diameters equal to 1/85, 1/43 and 1/29inch, respectively. Each of these catalysts was loaded into reactors andused to hydroconvert Cold Lake Crude, the properties of which are givenin Table VI. Conditions for the tests were 775° F., 2250 psig, 2.6V/Hr./V and 6000 SCF/B hydrogen gas rate. Product inspections wereobtained after 20 hours on oil and are shown below:

    ______________________________________                                        Catalyst Size, Inch                                                                            1/85     1/43     1/29                                       ______________________________________                                        Sulfur, Wt.%      0.37     0.37    0.40                                       Asphaltenes, Wt.%                                                                              1.1      2.3       3.5                                       Nickel, ppm      3.1      5.9      11.2                                       Vanadium, ppm    1.0      9.0      19.1                                       ______________________________________                                    

These data show that the asphaltene, nickel and vanadium removalreactions are strongly dependent upon catalyst particle size indicatingstrong diffusion limitations. On the other hand, sulfur appears to bemuch less dependent upon particle size. It is found from these data thatas particle size increases it is desirable to increase the size of thepores to decrease the diffusion limitations with larger particles. Onthe other hand, as particle size is decreased it is desirable todecrease the pore size, since less diffusion resistance will beencountered. Thus, larger particles (e.g., 1/16 inch) will requirelarger pores (e.g., 175-275A) and smaller particles (e.g., 1/64 inch)will require smaller pores (e.g., 100-200A) while intermediate particles(e.g., 1/32 inch) will require intermediate pores (e.g., 150-250A).

The following examples show that R-1 catalyst can be used to treat 1050°F.+ in heavy crudes or residua at a variety of conditions ranging fromhydrotreating, with minor conversion of the 1050° F.+ materials, throughhydroconversion conditions wherein a major amount of the 1050° F.+material is converted to lower boiling products.

EXAMPLES 23-29

Catalyst D, the R-1 catalyst of Example 5, having an average particlesize of 1/32 inch, was used for treating Jobo Crude (Table VI) in aseries of runs wherein the severity of the reaction was graduallyincreased principally by a combination of decreased space velocity andincreased temperature to obtain increasing rates of conversion. InExamples 23-26 the start-of-run (SOR) temperature was set at 650° F.,and gradually increased during the operation to maintain a givenreaction rate. In Examples 27-19, the start-of-run temperature was 700°F. These and other conditions of operation of the several runs, and theinspections obtained on the products of the series of reactions aregiven in Table X, below. Data are shown for Examples 23-26 at 662° F.after 517 hours on oil. Data for Examples 27-29 are at 736° F. after 805hours on oil. In this series of runs, Examples 23 through 26 can beconsidered as essentially hydrotreating runs, and Examples 27 through 29as hydroconversion runs.

                                      TABLE X                                     __________________________________________________________________________              Pressure, psig          2250                                                  Hydrogen Rates, SCF/Bbl.                                                                              6000                                                  Temperature, ° F. (SOR)                                                 Examples 17-20          650                                                   Examples 21-23          700                                        Example No.  23   24   25   26   27   28   29                                 __________________________________________________________________________    Space Vel., V/H/V                                                                          0.79 0.59 0.39 0.19 0.98 0.49 0.24                               Product Inspections                                                            Gravity, ° API                                                                     12.4 13.4 14.1 16.0 15.4 18.1 21.4                                Sulfur, Wt.%                                                                              2.56 2.23 1.87 1.11 1.45 0.78 0.15                                Nitrogen, Wt.%                                                                            0.65 0.62 0.60 0.55 0.56 0.49 0.26                                Con. Carbon, Wt.%                                                                         10.4 11.0 10.3 7.9  8.3  6.3  3.8                                 Asphaltenes, Wt.%                                                                         10.6 10.0 9.3  5.4  7.8  4.2  --                                  Metals, ppm                                                                    Ni         52.2 48.2 38.9 29.5 28.3 16.1 5.1                                  V          242.6                                                                              207.2                                                                              183.0                                                                              107.5                                                                              143.4                                                                              72.0 0.8                                 1050° F.+, Conv.,                                                       Wt.%       1.8  12.1 7.5  13.4 21.9 33.4 46.6                                1050° F.+  Quality                                                      Sulfur, Wt.%                                                                             3.47 3.09 2.83 1.89 2.51 1.49 0.30                                 Con. Carbon,                                                                  Wt.%       23.3 22.7 20.4 17.5 21.3 18.4 10.4                                 Metals, ppm                                                                    Ni        108.6                                                                              112.5                                                                              97.9 65.4 86.2 59.0 8.7                                   V         504.4                                                                              476.0                                                                              391.5                                                                              248.3                                                                              341.5                                                                              196.8                                                                              9.5                                 Metal on Cat. Wt.%*                                                                       115  60   75   --   168  100  --                                 __________________________________________________________________________     *Wt.% on fresh catalyst at end of operation.                             

These data thus show that relatively high temperature is required toobtain high rates of hydroconversion of the 1050° F.+ materials, andconversely that low temperatures cannot provide adequate conversionrates, even with relatively low space velocities. The product ofExamples 23 through 26 is unsuitable for coker feed because the metalscontent is too high, and unsuitable even as fuel because of the highsulfur content. The product of Example 26 is of marginal utility as acoker feed, but coke produced from such product would necessarily be ofpoor quality. The sulfur content is too high for use as fuel, andfurther treatment is required to render the product suitable as a fueloil. As to the series of hydroconversion reactions, the data show thatthe product of Example 29 is of good quality, and even suitable as afeed for a resid catalytic cracker using amorphous silica-aluminacatalysts. The product of Examples 28 and 29 can be split into 1050° F.+and 1050° F.- fractions, and the 1050° F.+ fraction coked as presentedin Example 30 below. Best use of the Example 28 product requires that itbe treated in R-2 service to obtain a material having from 2 to 3 wt.%Con. carbon and <5 ppm metals, preferably <2 ppm metals, which materialcan then serve as a prime feed for a conventional hydrocracker orcatalytic cracker. The product of Example 29 is a marginal feed for aconventional hydrocracker or catalytic cracker. The product of Example29 is a prime feed for a resid catalytic cracker as presented in Example38.

The product of Example 27 is marginally suitable for R-2 service, or asa marginal feed for use in a coker. None of the products of Examples 27through 29 is suitable for direct use in a conventional hydrocracker orcatalytic cracker.

The following example illustrates certain advantages in use of theproduct of Example 29 as coker feed.

EXAMPLE 30

Case A: Jobo crude was split into two fractions, 1050° F.+ and 1050° F.-fractions. Yields for coking the 1050° F.+ fraction were predicted usingcorrelations. The total yields were then calculated by mathematicalblending.

Case B: The Example 29 product was separated into 1050° F.+ and 1050°F.- fractions. Yields for coking the 1050° F.+ fraction were predictedusing correlations. The total liquid yields were calculated bymathematical blending.

The results of these calculations are given in Table XI below:

                  TABLE XI                                                        ______________________________________                                        Basis: 50 MB/D of Jobo Crude                                                               Case A     Case B                                                ______________________________________                                        C.sub.3, M Lb./D                                                                             0.87         0.44                                              C.sub.4, B/D   893          777                                               C.sub.5 /430° F., B/D                                                                 4,434        3,446                                             430/650° F., B/D                                                                      8,323        11,950                                            650/1050° F., B/D                                                                     28,108       31,703                                            Coke, T/D      1,223 (5.9% S)                                                                             373 (2.5% S)                                      C.sub.3 .sup.+ Yield, Vol.%                                                                   86           97                                               ______________________________________                                    

These comparative data show that the C₃ ⁺ volume percent yield ofproduct is 97 when coking the 1050° F.+ product of Example 29 vis-a-visthe 86 C₃ ⁺ volume percent yield obtained when coking the 1050° F.+material of the Jobo crude per se, an 11 volume percent improvement inC₃ ⁺ liquid yield. Moreover, both the coke and the liquid productresulting from coking the Example 29 1050° F.+ material vis-a-vis the1050° F.+ material from the original Jobo crude is superior.

The following presents a series of runs which show that products can beproduced from 1050° F.+ heavy crudes and residua by reaction with an R-1catalyst which are admirably suitable as feeds for R-2 service. In thefollowing series of data, the initial temperature of the several runs isfurther increased as contrasted with the runs of preceding Examples 27through 29. The space velocity is then gradually decreased, and as spacevelocity is lowered, it will be observed that product quality improves.

EXAMPLE 31

A series of runs, viz., Example 31, Runs 1-4, was conducted using an R-1type catalyst, identical to Catalyst D previously described (Example 5),except that the catalyst contained 0.3 Wt.% Sn (by impregnation) inaddition to cobalt and molybdenum. Again particles averaging 1/32 inchdiameter were used. Jobo crude (Table V) was contacted in each instancewith the catalyst at a start-of-run temperature of 760° F., thetemperature being increased during the operations at an average rate offrom about 1.8 to 2.2° F. per day to maintain a substantially constantrate of reaction for a given run. The following data, given in TableXII, below, were obtained at a temperature of 765° F. after 166 hours onoil.

                  TABLE XII                                                       ______________________________________                                        Pressure, psig          2250                                                  Hydrogen Rate, SCF/Bbl  6000                                                  Run No.         1       2       3     4                                       ______________________________________                                        Space Velocity, V/Hr./V                                                                       1.90    1.45    0.91  0.46                                    Product Inspection                                                             Gravity, ° API                                                                        17.3    17.3    18.5  20.7                                     Sulfur, Wt.%   1.29    1.08    0.80  0.20                                     Con Carbon, Wt.%                                                                             7.6     7.0     7.1   4.0                                      Asphaltenes, Wt.%                                                                            6.1     6.2     4.8   1.9                                      Metals, ppm                                                                    Ni            29.2    24.8    17.2  2.7                                       V             26.1    93.9    46.9  0.9                                      1050+ ° F., Conv., Wt.%                                                               44.3    38.2    43.5  56.6                                     1050+ ° F., Quality                                                     Sulfur, Wt.%  1.98    1.81    1.48  0.43                                      Con Carbon, Wt.%                                                                            26.0    21.7    24.3  17.2                                      Metals, ppm                                                                    Ni           96.8    73.5    64.5  20.6                                       V            363.4   308.0   189.0 1.5                                      Metal on Cat., Wt.%*                                                                         69      88      91    46                                      ______________________________________                                         *Wt.% on fresh cat at end of operation. Runs terminated at different time     on oil.                                                                  

It is thus apparent by reference to Runs 3 and 4, as contrasted withRuns 1 and 2, that temperatures above about 750° F., at space velocitiesabout 1, can provide an R-2 feed of desirable quality. Suitably, the R-2feed is about 90 Wt.% demetallized, and hence the product of R-1 serviceis usually one containing metals below about 60 ppm, which metalscontent can be further reduced in R-2 service to 5 ppm or less. Also,Con. carbon at levels of about 7 Wt.% can be reduced to levels rangingabout 2-3 Wt.% as required for use in R-2 service. In operating at theseconditions, the R-1 catalyst was found suitable for about 3-4 weeks ofcontinuous R-1 service.

The product of Example 31, Run 4, on the other hand, can be fed directlyto a catalytic cracker employing zeolite catalyst as shown by referenceto Example 38, if desired. The product produced in Example 29, describedby reference to Table X, is a prime feed for resid catalytic cracking asshown in Example 38.

EXAMPLE 32

Several catalysts of varying pore size distribution were obtained fordemonstrative purposes. Catalysts S and T are commercially availablealumina which was impregnated with cobalt and molybdenum salts and thendried and calcined at conditions similar to that used in Example 9.Catalyst V, the catalyst of the invention, was prepared in a mannersimilar to that used for Catalyst D described by reference Example 5. Aportion of each having an average particle size of 1/32 inch was thenemployed in a fixed bed reactor for hydroconversion of whole Jobo crudeto measure the effectiveness of each in R-1 service. The pore sizedistributions of each of these several catalysts, termed Catalysts S, T,U, and V for convenience, the conditions under which the hydroconversionruns were conducted, and product data are tabulated in Table XIII, asfollows:

                  TABLE XIII                                                      ______________________________________                                        (a) Description of Catalysts:                                                 Catalyst       S       T       U       V                                      ______________________________________                                        Surface Area, m.sup.2 /g                                                                     250     217     259.sup.(1)                                                                           362                                    Pore Volume, cc/g                                                                             0.55    0.53   0.58.sup.(1)                                                                          1.51                                   Pore Volume                                                                   Distribution, %                                                                0-50A Pores   4.3     10.7    5.0      2.8                                    50-150A       73.8    33.0    40.5    15.7                                    150-250A      12.2    22.6    33.1    25.2                                    250-350A      5.4     16.8    15.4    27.3                                    350A+         4.3     16.9    6.1     29.1                                    % CoO          3       3       6       6                                      % MoO.sub.3    13      21      20      20                                    (b) Process Conditions:                                                        Temperature, ° F.                                                                         789 (after 665 hours on                                                       oil, 750° F. SOR)                                   Space Velocity, V/Hr./V                                                                          1.0                                                        Pressure, psig     2250                                                       Gas Rate, SCF/Bbl 6600                                                       (c) Product Inspections:                                                      Catalyst       S       T       U       V                                      ______________________________________                                        Product Inspection                                                             Sulfur, Wt.%  1.163   1.254   1.588   1.074                                   Metals, ppm                                                                    Ni           27.9    28.1    23.8    21.1                                     V            72.1    83.1    49.9    38.0                                    Metal on Cat., Wt.%*                                                                         43      41      62      99                                    ______________________________________                                         .sup.(1) Data obtained from pore size distribution measurement due to         problem with single point nitrogen measurements for surface area and pore     volume.                                                                       *Wt.% on fresh cat at 665 hours on oil.                                  

These data thus show that Catalyst V, an R-1 catalyst, which, interalia, contains greater than 20% of its total pore volume in the 150A to250A range, less than 5% of its pore volume in 0-50A pores and less than30% of its pore volume in the 350A+ range, is far superior to the othercatalysts, none of which are R-1 catalysts, in terms of both sulfur andmetals removal, but particularly as relates to metals removal. In termsof metals removal, an average of about 35% less of Catalyst V isrequired to remove the same amounts of metals as would be removed by theother catalysts.

The following example shows that as total pore volume in the 150-250Arange is increased, the catalyst becomes even more effective in terms ofremoving metals.

EXAMPLE 33

The following data are illustrative of that obtained from two differentR-1 catalysts, one (Catalyst W) of which contains 56.7% of the pores inthe 150-250A range and the other (Catalyst D), also described byreference to Table I except that it contains 0.3 wt.% Sn, byimpregnation) of which contains 44.1% of its total pore volume in poresizes ranging 150-250A. Each is used at similar conditions for thehydroconversion of Cold Lake Crude (Table VI). Catalyst W was preparedsimilarly to Catalyst C except that La was not included. The gel wasimpregnated by the methods of Example 9. Both catalysts were constitutedof particles averaging 1/32 diameter. The description of these catalystsin terms of their pore size distributions, the conditions of the run andthe inspections on the products from the runs are given in Table XIVbelow:

                  TABLE XIV                                                       ______________________________________                                                (a) Description of catalyst:                                          Catalyst          W         D                                                 ______________________________________                                        Surface Area, m.sup.2 /g                                                                        271.sup.(1)                                                                             330                                               Pore Volume, cc/g 1.22.sup.(1)                                                                             1.23                                             Pore Volume Distribution, %                                                    0-50A            --        1.5                                                50-150A           3.0      15.5                                               150-250A         56.7      44.1                                               250-350A         25.3      33.0                                               350A+            15.0      5.9                                                % CoO             6         6                                                 % MoO.sub.3      20        20.5                                                      (b) Process Conditions:                                               Temperature,° F.                                                                         750° F.                                                                          (210-240 hours                                    Pressure, psig    2250      on oil)                                           Hydrogen Rate, SCF/Bbl.                                                                         6000                                                        Space Velocity, V/Hr./V                                                                          0.5                                                                (c) Product Inspections:                                              Catalyst          W         D                                                 ______________________________________                                        Gravity, ° API                                                                           23.4      24.0                                              Sulfur, Wt.%       0.16      0.09                                             Con Carbon, Wt.%  2.5       2.1                                               Asphaltenes, Wt.% 0.9       1.2                                               Metals, ppm (Ni and V)                                                                          2.0       5.8                                               1050° F.+                                                               Sulfur, Wt.%      0.29      0.26                                              Con Carbon, Wt.% 8.0       9.7                                                Metals, ppm                                                                    Ni              1.7       6.6                                                 V               4.7       9.3                                               ______________________________________                                         .sup.(1) Data obtained from pore size distribution measurements due to        problems with nitrogen measurements for surface area and pore volume.    

The advantages of maximizing pores within the 150-250A pore diameterrange for demetallization is thus clearly illustrated. Catalysts similarto Catalyst W, but with higher pore volume in the 150-250A pore diameterrange, and greater surface area, provide even greater improvements.

The following additionally shows that a Group IVA metal is effective inincreasing the rate of demetallization of the catalysts of thisinvention.

EXAMPLE 34

Two catalysts were prepared, each at the same conditions and identicalin composition one to the other, except that one contained 3 Wt.%germanium by impregnation and the other did not. These catalysts,identified as Catalyst V and V', are similar in their composition(except as to the presence of germanium in Catalyst V') and in theirphysical characteristics as relates to pore volume and pore sizedistribution, and method of preparation which is the same as that ofCatalyst D identified by reference to Table I. Average particle size forboth catalysts was 1/32 inch. Each catalyst was employed for thehydroconversion of Jobo crude, at conditions very similar to those usedin Example 32 to provide products as identified in Table XV, below:

                  TABLE XV                                                        ______________________________________                                        Process Conditions:                                                            Temperature, ° F.                                                                     778° F.                                                                          (496 hours on oil)                                   Pressure, psig 2250                                                           Space Velocity, V/H/V                                                                        1.0                                                            Hydrogen Rate, SCF/B                                                                         6000                                                          Catalyst          V          V'                                               ______________________________________                                        Promoter          None       3% Ge                                            Product Inspection                                                             Sulfur, Wt.%     1.098      1.308                                             Metals, ppm                                                                    Ni              19.4       14.6                                               V               34.1       23.1                                             ______________________________________                                    

The rate of demetallization of Catalyst V' used for hydroconversion ofthe crude is thus appreciably increased as contrasted with Catalyst Vwhich does not contain the germanium promoter.

The following examples are exemplary of an R-2 catalyst of preferredcomposition, the catalyst being described as used in a typical R-2service situation for hydroconversion of an R-1 product resultant fromthe treatment of a whole Jobo crude by contact with R-1 catalyst attypical R-1 service conditions. The performance of the R-2 catalyst iscompared with an R-1 catalyst for similar use, and with a commerciallyavailable catalyst in similar service.

EXAMPLE 35

Runs were made wherein whole Jobo crude (Table VI) was introduced intoan R-1 reactor containing a fixed bed of R-1 catalyst (Catalyst V) andtreated at hydroconversion conditions, the R-1 product produced beingdefined in Column 2 of Table XVI, below:

                  TABLE XVI                                                       ______________________________________                                        (a) Conditions of Operation:                                                  R-1 Reactor:                                                                   Temperature, ° F.                                                                           750 (SOR)                                                Pressure, psig       2250                                                     Hydrogen Rate, SCF/Bbl.                                                                            6000                                                     Space Velocity, V/H/V                                                                              1.0                                                     (b) R-1 Product:                                                              Gravity, ° API 16.8                                                    Sulfur, Wt.%           1.40                                                   Carbon, Wt.%          86.44                                                   Hydrogen, Wt.%        11.25                                                   Con. Carbon, Wt.%     --                                                      Asphaltenes, Wt.%      5.49                                                   Metals, ppm                                                                    Ni                   24.6                                                     V                    39.7                                                    Nitrogen, Wt.%         0.577                                                  Distillation, Wt.%                                                             IBP                  300                                                      5%                   455                                                      10                   515                                                      20                   600                                                      30                   675                                                      40                   747                                                      50                   825                                                      60                   944                                                      % Recovered           65                                                      % Residue             35                                                      FBP                  1047                                                    ______________________________________                                    

The R-1 product, characterized in Table XVI (b), was then successivelypassed over Catalyst V (Example 34), having particles averaging 1/32inch diameter, at a start-of-run temperature of 750° F., 6000 SCF/BblH₂, 2250 psig and with space velocities varying from 0.49 to 1.93V/Hr./V. Data shown in Table XVII are for products withdrawn from thereactor at 755° F. after 161 hours on oil.

                  TABLE XVII                                                      ______________________________________                                        V/Hr./V         0.49    0.83    0.95  1.93                                    Product Inspections                                                            Gravity, ° API                                                                        23.5    19.8    18.3  17.5                                     Sulfur, Wt.%   0.10    0.38    0.71  1.05                                     Asphaltenes, Wt.%                                                                            0.86    2.48    3.88  4.32                                     Metals, ppm                                                                    Ni            1.7     9.5     14.6  18.0                                      V             0.1     0.3     5.7   37.3                                    ______________________________________                                    

These results show that the R-1 type of catalyst is not ideally suitedfor R-2 service. High temperatures and low space velocities are requiredto reach the R-2 catalyst target of <5 ppm metals and 2-3 Wt.% Con.carbon (<1 Wt.% asphaltenes).

A catalyst with maximum pores in the 100-200A range is preferred for R-2service as shown in the next example. In addition, it is preferred tooperate at lower temperature where equilibrium favors aromaticssaturation enhancing Con Carbon removal.

EXAMPLE 36

The R-1 product characterized in Table XVI (b) was successively passedover Catalyst V and a commercially available hydrotreating Catalyst Xwhich is characterized in Table XVIII (a). The catalysts, averaging 1/32inch in particle diameter, were evaluated at a start-of-run temperatureof 700° F., 6000 SCF/B H₂, 2250 psig and 0.5 V/Hr./V. Data shown inTable XVIII (b) are for products withdrawn from the reactor at 700° F.after 93 hours on oil.

                  TABLE XVIII                                                     ______________________________________                                        (a) Description of Catalyst X                                                 Surface Area, m.sup.2 /g  222                                                 Pore Volume, cc/g         0.58                                                Pore Volume Distribution, %                                                    0-50A Pores              1.6                                                  50-100A                  32.9                                                 100-200A                 51.8                                                 200-300A                 9.0                                                  300A+                    4.7                                                 % NiO                     3.0                                                 % MoO.sub.3               18.0                                                (b) Characterization of R-2 Product                                           Catalyst            X         V                                               ______________________________________                                        Product Inspection                                                             Gravity, ° API                                                                            20.7      19.8                                             Sulfur, Wt.%       0.207     0.282                                            Asphaltenes, Wt.%  0.83      1.29                                             Metals, pm                                                                     Ni                7.7       8.4                                               V                 0.1       0.1                                             ______________________________________                                    

The data show that the commercial Ni/Mo catalyst with 52% of its poresin the 100-200A region is more active for sulfur, asphaltene and metalsremoval at the conditions than the R-1 catalyst which has less of itspores in 100-200A region.

The catalyst of the invention for R-2 service wherein pores in the100-200A region are further maximized is shown to be superior to thecommercially available catalyst (Catalyst X) in Example 37.

EXAMPLE 37

The R-1 product (Table XVI (b)) was successively passed over Catalyst X(Commercial catalyst of Example 36) and Catalyst P (Example 9), havingaverage particle size diameters of 1/32 inch, at 650° F. start-of-runtemperature, 6000 SCF/B H₂, 2550 psig and 0.5 V/Hr./V. Catalyst Y ischaracterized in Table XIX (a) and the product inspection for productwithdrawn at 650° F. after 48 hours on oil is shown in Table XIX.

                  TABLE XIX                                                       ______________________________________                                        (a) Description of Catalyst Y                                                 Surface Area, m.sup.2 /g                                                                             212                                                    Pore Volume, cc/g      0.43                                                   Pore Volume Distribution, %                                                    0-50A Pores           8.1                                                     50-100A               19.4                                                    100-200A              58.3                                                    200-300A              13.1                                                    300A+                 1.1                                                    % NiO                   6                                                     % MoO.sub.3             20                                                    (b) Characterization of R-2 Product                                           Catalyst          X        Y        P                                         ______________________________________                                        Product Inspection                                                             Gravity,° API                                                                           18.5     18.6     18.8                                       Sulfur, Wt.%     0.436    0.533    0.287                                      Asphaltenes, Wt.%                                                                              2.1      2.5      1.7                                        Metals, ppm                                                                    Ni              9.4      9.0      6.0                                         V               2.8      0.9      0.7                                       ______________________________________                                    

These data thus show the advantage for having less than 10% of the porevolume in 0-50A pores and greater than 55% of the pore volume in100-200A pores and less than 25% of its pores in 300A+ pores. Catalyst Ywith 58% of its pores in the 100-200A region shows some advantage fordemetallization over Catalyst X which had 52% of its pore volume in100-200A pores. Both were Ni/Mo catalysts. Catalyst P, a Co/Mo catalystwith 58% of its pore volume in 100-200A pores and 3.7% of its porevolume in 0-50A pores and 1.6% of its pores in 300A+ pores was the mostoutstanding catalyst for R-2 service.

EXAMPLE 38

The conditions for the R-1 reactor can be varied to yield product whichis suitable for coking, for resid catalytic cracking by contact withamorphous silica alumina (3A), for use in zeolite catalytic cracking orfor further treatment in the R-2 reactor to produce a product containing<5 ppm metals, preferably <2 ppm metals, with a Con. carbon of less then3 wt.%. The material from R-2 service is suitable for conversion in aconventional catalytic cracking or hydrocracking unit. Results of suchruns are summarized in Table XX, below:

                                      TABLE XX                                    __________________________________________________________________________    Jobo Feed - 2250 psig, 6000 SCF/B H.sub.2                                                                      R-1   R-1/R-2                                                     R-1   R-1   Plus  Plus                                                        Plus  Plus  Zeolytic                                                                            Zeolytic                               Process          Coking                                                                            Coking                                                                              3A C/C                                                                              C/C   C/C                                    __________________________________________________________________________    R-1 Conditions                                                                 SOR Temp.,° F.                                                                         --  700   700   760   760                                     Space Velocity,                                                                V/Hr./V        --  0.4   0.25  0.5   1.0                                    Avg. R-1 Product                                                               Sulfur, Wt.%    --  0.67.sup.(1)                                                                        0.32.sup.(1)                                                                        0.22.sup.(2)                                                                        0.76.sup.(2)                            Metals, ppm     --   62    10    5     60                                     Con. Carbon, Wt.%                                                                             --  5.3   3.8   4.0   6.5                                    Catalytic Cracking Conditions                                                  430° F..sup.+ Conv., %                                                                 --  --     25    80    80                                     Catalyst Addition                                                              Rate, Lb./B    --  --    --    1.0   0.4                                    Estimated Yields                                                               C.sub.3.sup.+, Vol.%                                                                          86   97    97   107   110                                     Coke, Wt.%      13.8                                                                              4.4   7.5.sup.(3)                                                                         7.5.sup.(3)                                                                         6.7.sup.(3)                             Sulfur in Coke, Wt.%                                                                           5.9                                                                              2.5   --    --    --                                     __________________________________________________________________________     .sup.(1) Analyses averaged for total run; life expected to be greater tha     2 months.                                                                     .sup.(2) Analyses averaged for total run; life expected to be 3-4 weeks.      .sup.(3) Coke make on cat cracking (C/C) catalyst.                       

These data show that coking of raw Jobo crude results in 86 vol.% yieldof C₃ ⁺ and a 13.8 wt.% yield of sour coke (5.9% S). When the crude istreated in R-1 at 700° F. and at 0.4 V/Hr.V, the product is a primecoker feed. Coking the feed increases the C₃ ⁺ yield to 97 vol.% andreduces the coke to 4.4% (2.5% S). Published data and correlations showthat if the severity of R-1 is increased by reducing the space velocityto 0.25 V/Hr./V, the product is then suitable for resid catalyticcracking using amorphous SiO₂ /Al₂ O₃ catalyst. The yields produced are97 vol.% C₃ ⁺ and 7.5 wt.% coke. If the severity of R-1 is furtherincreased to 760° F. and 0.5 V/Hr./V, the product is suitable forcatalytic cracking using zeolite cracking catalyst. In this instance,the yields produced are 107 vol.% C₃ ⁺ and 7.5 wt.% coke. Moreover,using the preferred reaction sequences of R-1/R-2 catalysts, thisproduct can be catalytically cracked using zeolite catalysts to produceyields of 110 vol.% C₃ ⁺ and 6.7 wt.% coke. These results show the wideversatility and capabilities of these catalysts and processes.

It is apparent that various modifications and changes can be madewithout departing the spirit and scope of the present invention.

Pore size distributions, as percent of total pore volume, for purpose ofthe present invention are measured by nitrogen adsorption whereinnitrogen is adsorbed at various pressures using the Aminco AdsorptomatCat. No. 4-4680, and multiple sample accessory Cat. No. 4-4685. Thedetailed procedure is described in the Aminco Instruction Manual No.861-A furnished with the instrument. A description of the Adsorptomatprototype instrument and procedure is given in Analytical Chemistry,Volume 32, page 532, April, 1960.

An outline of the procedure is given here, including sample preparation.

From 0.2 to 1.0 g. of sample is used and the isotherm is run in theadsorption mode only. All samples are placed on the preconditionerbefore analysis where they are out-gassed and dried at 190° C undervacuum (10⁻ ⁵ torr) for 5 hours. After pretreatment the weighed sampleis charged to the Adsorptomat and pumped down to 10⁻ ⁵ torr. At thispoint, the instrument is set in the automatic adsorption mode to chargea standard volume of gas to the catalyst. This is done by charging apredetermined number of volumes as doses and then allowing time foradsorption of the nitrogen to reach equilibrium pressure. The pressureis measured in terms of its ratio to the saturation pressure of boilingliquid nitrogen. Three doses are injected and 8 minutes allowed forequilibration of each measured relative pressure. The dosing andequilibration are continued until a pressure ratio of 0.97 is exceededand maintained for 15 minutes. The run is then automatically terminated.

The data obtained with the dead space factor for the sample, the vaporpressure of the liquid nitrogen bath, and the sample weight are sent toa digital computer which calculates the volume points of the isotherm,the BET area, and the pore size distribution of the Barrett, Joyner, andHalenda method. [Barrett, Joyner, and Halenda, J. Am. Chem. Soc. 73, p.373.] It is believed that the Barrett, Joyner, and Halenda method is ascomplete a treatment as can be obtained, based on the assumptions ofcylindrical pores and the validity of the Kelvin equation.

Hydrocarbon or hydrocarbonaceous feedstocks which can be treatedpursuant to the practice of this invention include heavy petroleumcrudes, synthetic crudes derived from coal, shale, tar sands, heavy oilsand tars which contain relatively high concentrations of asphaltenes,high carbon:hydrogen ratios, high metals contents, considerable amountsof sand and scale, considerable amounts of 1050° F.+ materials, andgenerally high sulfur and nitrogen.

Having described the invention, what is claimed is:
 1. A catalyst havingenhanced selectively suitable for the conversion and demetallization offeeds which contain large quantities of 1050° F.+ hydrocarbon materialscomprising a composite of from about 5 to about 50 percent of a GroupVIB metal, or compound thereof thermally decomposable to an oxide, orfrom about 1 to about 12 percent of a Group VIII metal, or compoundthereof thermally decomposable to an oxide, or a composite whichcomprises an admixture of said Group VIB and Group VIII metals, orcompounds thereof thermally decomposable to oxides, measured as oxides,and a porous inorganic oxide support, said catalyst comprising, when thecatalyst is of size ranging 1/500 to 1/50 inch average particle sizediameter, at least about 20 percent of its total pore volume of absolutediameter within the range of about 100A to about 200A; when the catalystis of size ranging from about 1/50 inch up to 1/25 inch average particlesize diameter, at least about 15 percent of its total pore volume ofabsolute diameter within the range of about 150A to about 250A; when thecatalyst is of size ranging from about 1/25 inch to about 1/8 inchaverage particle size diameter, at least about 15 percent of its totalpore volume of absolute diameter within the range of about 175A to about275A; surface areas ranging at least about 200 m² /g to about 600 m² /gand pore volumes ranging from about 0.8 cc/g to about 3.0 cc/g.
 2. Thecatalyst of claim 1 wherein the catalyst of particle size diameterranging from about 1/500 to 1/50 inch particle size diameter ischaracterized as follows:

    ______________________________________                                        Distribution of Pore Diameters                                                0-50A                 <20%                                                    100-200A              >20%                                                    300A                  <30%                                                    Pore Volume, cc/g     0.8-1.4                                                 Surface Area, m.sup.2 /g                                                                            300-450                                                 ______________________________________                                    


3. The catalyst of claim 1 wherein the catalyst of particle sizediameter ranging from about 1/500 to 1/50 inch particle size diameter ischaracterized as follows:

    ______________________________________                                        Distribution of Pore Diameters                                                0-50A                 <10%                                                    100-200A              >25%                                                    300A+                 <25%                                                    Pore Volume, cc/g     0.9-1.5                                                 Surface Area, m.sup.2 /g                                                                            310-500                                                 ______________________________________                                    


4. The catalyst of claim 1 wherein the catalyst of particle sizediameter ranging from about 1/500 to 1/50 inch particle size diameter ischaracterized as follows:

    ______________________________________                                        Distribution of Pore Diameters                                                0-50A                 <2%                                                     100-200A              >70%                                                    300A+                 <1%                                                     Pore Volume, cc/g     1.1-1.7                                                 Surface Area, m.sup.2 /g                                                                            325-550                                                 ______________________________________                                    


5. The catalyst of claim 1 wherein the catalyst of particle sizediameter ranging from about 1/50 to 1/25 inch particle size diameter ischaracterized as follows:

    ______________________________________                                        Distribution of Pore Diameters                                                0-50A                 <10%                                                    150-250A              >15%                                                    350A+                 <35%                                                    Pore Volume, cc/g     1.1-1.7                                                 Surface Area, m.sup.2 /g                                                                            320-475                                                 ______________________________________                                    


6. The catalyst of claim 1 wherein the catalyst of particle sizediameter ranging from about 1/50 to 1/25 inch particle size diameter ischaracterized as follows:

    ______________________________________                                        Distribution of Pore Diameters                                                0-50A                 <5%                                                     150-250A              >20%                                                    350A+                 <30%                                                    Pore Volume, cc/g     1.3-1.9                                                 Surface Area, m.sup.2 /g                                                                            340-575                                                 ______________________________________                                    


7. The catalyst of claim 1 wherein the catalyst of particle sizediameter ranging from about 1/50 to 1/25 inch particle size diameter ischaracterized as follows:

    ______________________________________                                        Distribution of Pore Diameters                                                0-50A                 <1%                                                     150-250A              >45%                                                    350A+                 <7%                                                     Pore Volume, cc/g     1.5-2.1                                                 Surface Area, m.sup.2 /g                                                                            360-600                                                 ______________________________________                                    


8. The catalyst of claim 1 wherein the catalyst of particle sizediameter ranging from about 1/25 to 1/8 inch particle size diameter ischaracterized as follows:

    ______________________________________                                        Distribution of Pore Diameters                                                0-50A                 <5%                                                     175-275A              >15%                                                    350A+                 <40%                                                    Pore Volume, cc/g     1.3-1.9                                                 Surface Area, m.sup.2 /g                                                                            340-500                                                 ______________________________________                                    


9. The catalyst of claim 1 wherein the catalyst of particle sizediameter ranging from about 1/25 to 1/8 inch particle size diameter ischaracterized as follows:

    ______________________________________                                        Distribution of Pore Diameters                                                0-50A                 <4%                                                     175-275A              >20%                                                    350A+                 <35%                                                    Pore Volume, cc/g     1.5-2.1                                                 Surface Area, m.sup.2 /g                                                                            350-600                                                 ______________________________________                                    


10. The catalyst of claim 1 wherein the catalyst of particle sizediameter ranging from about 1/25 to 1/8 inch particle size diameter ischaracterized as follows:

    ______________________________________                                        Distribution of Pore Diameters                                                0-50A                 <3%                                                     175-275A              >30%                                                    350A+                 <25%                                                    Pore Volume, cc/g     1.8-2.3                                                 Surface Area, m.sup.2 /g                                                                            370-650                                                 ______________________________________                                    


11. The catalyst of claim 1 wherein said catalyst comprises from about15 to about 25 percent of a Group VIB metal, or compound thereof, andfrom about 4 to about 8 percent of a Group VIII metal, or compoundthereof, or admixture of said Group VIB and Group VIII metals, orcompounds thereof, measured as oxides.